the ubiquity of ( hetero)arylamines 
 in natural products , pharmaceuticals , 
 agrochemicals , and organic materials inspires chemists to develop 
 efficient synthetic methodologies for constructing c 
traditional approaches for the synthesis of arylamines 
 involve nitration of arenes , followed by reduction . using strongly acidic nitric acid and harsh conditions 
 in these systems
metal - catalyzed 
 c  n cross - coupling reactions , such as the buchwald 
n 
 bond formation and are a powerful tool for organic chemists . despite these advances , the requirement for prefunctionalization 
 of arenes to aryl ( pseudo)halides or boronic acids as coupling partner 
 is inherently required .
recently , the dehydrogenative cross - coupling 
 of amines and aromatic 
 c  h moieties as coupling partners has emerged as a straightforward 
 pathway for the synthesis of ( hetero)arylamines , which has been 
 a complementary and potentially more effective process for the formation 
 of c 
n bonds . however , most cases 
 of metal - catalyzed c  h / n  h cross - coupling reactions 
 are limited to the use of expensive transition metals , such as pd , rh , and ru .
the amine reagents used in those amination reactions 
 can be classified as amines , amides , sulfonamides , n  o reagents , 
 or n  x ( x = halogen ) reagents .
interestingly , 
 phthalimide , which is a valuable ammonia equivalent and used to synthesize 
 primary amines , called the gabriel reaction , has recently captured much attention from chemists .
for example , 
 hartwig and co - workers documented a pd - catalyzed intermolecular c 
h 
 amination reaction of arenes with phthalimide to form n - aryl phthalimides using 6 equiv of phi(oac)2 as 
 an oxidant ( eq 1 ) .
deboef et al . were performed in 
 the presence of phi(oac)2 ( 2.55 equiv ) without 
 adding any metal species ( eq 2 ) . at the same time , li et al .
demonstrated 
 a rh(iii ) and ag cocatalyzed c  h amination of arenes bearing 
 directing groups using n - ots phthalimide as amidating 
 reagent ( eq 3 ) .
we wondered whether an 
 inexpensive copper catalyst and green and abundant molecular oxygen 
 as a terminal oxidant are feasible for the intermolecular amination 
 of indoles and 2-arylpyridines using phthalimide as the amine source 
 ( eq 4 ) .
recently , much effort has been directed toward exploring economical 
 and environmentally friendly catalysts , which led to various pioneering 
 advances in cu - mediated and cu - catalyzed direct c 
h amination 
 reactions . in this context , yu and co - workers 
 first reported the stoichiometric cu - mediated ar 
several improved cu - catalyzed inter- and intramolecular versions 
 were achieved by brasche and buchwald , li et al .
in addition , aminations of acidic c  h bonds of heterocycles 
 using catalytic cu / ligand or stoichiometric ag / base systems were independently 
 reported by mori et al . ,
, respectively , documented 
 cu - catalyzed direct aminations of aromatic c  h bonds using 
 removable directing groups .
however , in some cases , the use of a stoichiometric 
 amount of oxidant , such as silver species , n  o oxides , and 
 hypervalent iodine , is inevitable .
all of these pioneering studies 
 inspired us to pursue a simple cu / o2 catalytic system for 
 the sp c  h bond amination .
herein , we document 
 a cu - catalyzed c  h amidation of n - pyrimidyl(pyridyl ) 
 indoles and 2-arylpyridines under oxygen using phthalimide as an aminating 
 source ( eq 4 ) , which is complementary to the previously reported metal - catalyzed 
 c  h amination systems .
encouraged 
 by yu et al.s report , we began 
 our study by examining the reaction of n - pyrimidyl - substituted 
 indole 1a with phthalimide 2 in the presence 
 of cuoac ( 20 mol % ) under an oxygen atmosphere 
 at 150 c ( table 1 , entry 1 ) . to our delight , 
 the desired c 
a series of cu salts 
 examined during the optimization of reaction conditions showed a significant 
 role in promoting the sp c  h amination process . 

the use of cu(oac)2 , cu(otf)2 , and cu(opiv)2 also provided the desired amination product 3a with a slightly decreased yield compared to cuoac ( table 1 , entries 24 ) .
in contrast , cucl , cubr2 , and cucl2 showed no reactivity for this transformation 
 ( table 1 , entries 58 ) .
notably , running 
 reactions in the absence of a copper catalyst or under a nitrogen 
 atmosphere resulted in no aminated products , indicating that both 
 oxygen and the copper catalyst are critical for amination ( table 1 , entry 20 ) .
the screening of solvents indicated 
 that nonpolar solvents , including dce , anisole , o - dichlorobenzene , and chlorobenzene , efficiently promoted this transformation , 
 giving 6281% yields . on the contrary ,
performing reactions 
 in polar solvents , such as dmf , dmso , ch3cn , 1,4-dioxane , 
 and thf , resulted in nearly no desired product ( table 1 , entries 913 ) .
finally , the mixed solvent of toluene 
 and o - dichlorobenzene ( 1:1 ) produced the corresponding 
 aminated product 3a in 86% yield ( table 1 , entry 18 ) . by reducing the amount of catalyst from 20 to 
 10 mol % , a decreased yield ( 71% ) was observed ( table 1 , entry 19 ) .
hence , the optimal conditions are cuoac ( 20 mol 
 % ) and phthalimide ( 1.2 equiv ) under an o2 atmosphere at 
 150 c in toluene / o - dichlorobenzene ( 1:1 ) .
conditions : substrate 1a ( 0.3 mmol ) , phthalimide ( 0.36 mmol ) , cat .
( 20 mol % ) , solvent 
 ( 2 
 ml ) , o2 ( 1 atm ) , 150 c .
this protocol 
 for cuoac - catalyzed aromatic c  n coupling 
 via c  h activation is practical and efficient because green 
 molecular oxygen is used as oxidant , no additional additives are needed , 
 and the only byproduct is water . with these optimal conditions in 
 hand , we explored the scope and limitations of this method , as shown 
 in table 2 .
a wide range of electron - rich and 
 electron - poor substituted indoles bearing a pyrimidine directing group 
 were first examined under the standard conditions .
to our delight , 
 electron - donating groups such as me or meo , on either the indole ring 
 or the pyrimidine directing group , all provided the corresponding 
 amination products in moderate to good yields ( 5777% ) .
we 
 reasoned that electron - rich indole substrates are prone to proceeding 
 intermolecular polymization , and resulted 
 in moderate yield in meo - substituted substrate 3d .
substrates 
 with electron - withdrawing groups , including 5-f ( 1e ) , 
 5-cl ( 1f ) , 5-br ( 1 g ) , and 5-cn ( 1h ) , which could be used as functional handles for further transformations , 
 were subjected to the cu - catalyzed sp c  h amination 
 reaction , efficiently giving the amination products .
the strongly 
 electron - deficient no2-substituted indole 1i did not undergo amination under the standard conditions . besides 
 the pyrimidine group as a directing group , substrates with pyridine 
 as a directing group also worked well under the standard conditions 
 ( 3178% yields ) .
notably , the aldehyde group ( 1o ) was compatible in this system with 31% yield .
some byproducts were 
 observed possibly due to decarbonylation , oxidation , or polymerization 
 from 1o , but because of the complexity of byproducts 
 from 1o , structures could not be determined yet .
unexpectedly , 
 by switching the directing group from pyridyl to carbonyl group , n - benzoyl indole 1p gave the corresponding 
 product 3p , albeit with a low 27% yield .
other heterocycles , 
 such as benzo[d]oxazole and benzo[d]thiazole , were attempted , but no desired c 
conditions : substrate 
 ( 0.3 mmol ) , 
 phthnh ( 0.36 mmol ) , cuoac ( 20 mol % ) , o2 ( 1 atm ) , toluene / o - dichlorobenzene ( 1:1 , 2 ml ) , 150 c , 23 days .
encouraged by the success of a direct 
 c  h amination reaction 
 of indole derivatives , various substituted 2-arylpyridines were investigated 
 to further extend the generality of this approach .
as shown in table 3 , either electron - rich or electron - poor groups on 
 the aryl ring gave the corresponding products with moderate yields . 

we found that the efficiency of 2-arylpyridines or 2-arylpyrimidines 
 in this system was inferior to that of n - substituted 
 indoles .
for example , substrate 4a was subjected to the standard conditions to afford the monoaminated 5a as a major product in 53% yield along with 19% of recovered 4a . by further prolonging the reaction time , a trace amount 
 of bisamination product could be observed .
gratifyingly , electron - withdrawing 
 f ( 4f ) , cl ( 4 g ) , cf3 ( 4h ) , coome ( 4i ) , and cho ( 4j ) groups were 
 all well - tolerated under the standard conditions .
it is worth noting 
 that substrate 4e , containing an alkene group on the 
 aryl ring , performed in this case to provide the desired product 5e in 31% yield .
in addition , our efforts to apply the conditions 
 optimized for 2-pyrimidyl indole substrates to other types of substrates , 
 such as 2-(naphthalen-2-yl)pyridine and benzo[h]quinoline , were fruitful .
conditions : substrate ( 0.3 mmol ) , 
 phthnh ( 0.36 mmol ) , cuoac ( 20 mol % ) , toluene / o - dichlorobenzene 
 ( 1:1 , 2 ml ) , 34 days , o2 ( 1 atm ) , 150 c . to test the scope and limitations 
 of amines , the treatment of n - pyridyl indole 1k with saccharin 2b under the standard conditions 
 was first carried out .
as expected , 
 saccharin 2b worked well , giving the corresponding product 6a in 43% yield ( table 4 , entry 1 ) .
n - pyrimidyl indole 1a and 2-phenylpyridine 5a could also react with saccharin 2b ( table 4 , entries 24 ) . to our surprise ,
n 
 coupling product 6d , although with a low 22% yield ( table 4 , entry 5 ) .
we continued attempting other amine 
 reagents , such as 4-nitroaniline 2d and 2-amine pyridine 2e , while no obvious corresponding products were observed 
 ( table 4 , entries 5 and 6 ) .
therefore , there 
 is still a limitation in amine reagents , which are restricted to amides 
 with strong electron - withdrawing groups .
conditions : substrate ( 0.2 mmol ) , 
 cuoac ( 20 mol % ) , amine ( 0.2 mmol ) , toluene / o - dichlorobenzene ( 1:1 , 
 2 ml ) , 23.5 days , o2 ( 1 atm ) , 150 c . in order to gain an understanding of the mechanism 
 of this aromatic 
 c
first , 
 radical inhibitors , such as tempo , bht ( 2,6-di - tert - butyl-4-methylphenol ) , and 1,4-dinitrobenzene , were added to the 
 reaction under standard conditions , and no significant decrease in 
 yield was observed ( scheme 1 ) .
this result 
 suggests that a radical pathway for the c  h amination reaction 
 is possibly unlikely .
next , we investigated the kinetic isotope effect 
 via intermolecular and intramolecular competition experiments .
the 
 competition between substrate 4a and deuterated substrate [ d2]-4a under the standard conditions revealed a primary isotope 
 effect ( kie = 3.7 , scheme 2 , eq 5 ) .
an intramolecular 
 competition experiment using substrate [ d]-4a was further 
 measured , giving a kie of 2.1 ( scheme 2 , eq 
 6 ) .
these experiments indicated that the c  h bond activation 
 is a rate - determining step in the cu - catalyzed c 
h amination 
 reaction . on the basis of the above mechanistic studies and previous 
 findings , a tentative mechanism was proposed 
 as shown 
 in scheme 3 .
first , the in situ generation of the active cu(ii ) species occurs by oxidation with 
 o2 .
the coordination of pyrimidyl group in the substrate 1a to the copper(ii ) center is followed by the disproportionative 
 c  h activation reaction with another cu(ii ) species that produces 
 the aryl - cu(iii ) intermediate 8 and a cu(i ) species .
subsequently , phthalimide coordinates to the 
 aryl - cu(iii ) center and the reductive elimination of cu(iii ) intermediate 9 takes place to provide the corresponding aminated product 3a and a cu(i ) species , which would be oxidized by o2 under acidic conditions to regenerate the cu(ii ) species and water 
 as a byproduct .
nevertheless , at present , we can not completely exclude 
 a single electron transfer ( set ) pathway as proposed by yu et al .
in 
 conclusion , we have developed a simple and practical cu - catalyzed 
 c  h amination of n - pyrimidyl(pyridyl ) 
 indoles and 2-arylpyridines using phthalimide as an aminating source . 

the employment of inexpensive cuoac as the catalyst and molecular 
 oxygen as the terminal oxidant is a significant advantage for this 
 intermolecular transformation .
this reaction has the broad substrate 
 scope and shows moderate to good yields in most cases .
further exploration 
 of the generality and application of this approach is ongoing in our 
 lab .
toluene was dried and distilled before 
 use according to the standard method.h , c , and f nmr spectra were 
 obtained at 400 , 100 , and 400 mhz , respectively .
nmr spectra were 
 run in a solution of deuterated chloroform ( cdcl3 ) and 
 were reported in parts per million ( ppm ) .
abbreviations for signal 
 multiplicity are as follows : s = singlet , d = doublet , t = triplet , 
 q = quartet , p = pentet , m = multiplet , dd = doublet of doublet , etc . 

high - resolution mass spectra ( hrms ) were recorded 
 using electrospray ionization ( esi ) techniques .
n - substituted indole derivatives ( 1a1o ) were prepared according to the 
 literature procedure .
pyridine derivatives 
 ( 4a4s ) were prepared via suzuki 
 coupling with the corresponding boronic acids and 2-bromopyridines 
 according to the reported procedure . an oven - dried schlenk tube equipped with 
 a magnetic stir bar
was evacuated and backfilled with oxygen three 
 times . under oxygen , cuoac ( 0.06 mmol , 7.4 mg ) ,
indole derivatives 
 ( or 2-arylpyridine derivatives ) ( 0.3 mmol ) , and phthalimide ( 0.33 
 mmol , 48.5 mg ) were dissolved in the mixed solvent of toluene and o - dichlorobenzene ( 1:1 , 2 ml ) in the tube .
then , it was quenched 
 with naoh solution ( 10% , 10 ml ) and extracted with etoac ( 3  
 20 ml ) .
the combined organic layers were dried over na2so4 , filtered , and concentrated in vacuo .
yellow solid ( 88 mg , 86% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.43 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 232233 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.62 ( d , j = 8.8 hz , 1h ) , 
 8.45 ( d , j = 4.8 hz , 2h ) , 7.97 ( dd , j = 5.4 , 3.1 hz , 2h ) , 7.82 ( dd , j = 5.4 , 3.1 hz , 
 2h ) , 7.68 ( d , j = 7.6 , 1h ) , 7.417.37 ( m , 
 1h ) , 7.317.27 ( m , 2h ) , 6.96 ( t , j = 4.8 hz , 
 1h ) , 6.70 ( s , 1h ) ; c nmr ( 100 mhz , cdcl3 ) 
  167.9 , 158.3 , 157.6 , 135.9 , 134.7 , 132.5 , 127.6 , 125.4 , 125.0 , 
 124.2 , 122.8 , 121.4 , 117.3 , 116.0 , 109.6 ; ir ( kbr )  2926 , 2855 , 
 1727 , 1564 , 1452 , 1421 , 1241 , 1083 , 753 , 718 , 709 cm ; hrms ( esi+ , qtof ) exact mass calcd for c20h13n4o2 [ m + h ] 341.1039 , found : 
 341.1044 .
yellow solid ( 82 mg , 77% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.29 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 245247 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.56 ( d , j = 8.4 hz , 1h ) , 
 8.28 ( s , 2h ) , 7.977.95 ( m , 2h ) , 7.837.81 ( m , 2h ) , 
 7.87 ( d , j = 7.6 hz , 1h ) , 7.38 ( t , j = 8.4 hz , 1h ) , 7.27 ( t , j = 8.0 hz , 1h ) , 6.87 ( s , 
 1h ) , 2.20 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 ) 
  167.9 , 158.3 , 155.7 , 135.8 , 134.6 , 132.5 , 127.5 , 126.6 , 125.3 , 
 124.8 , 124.2 , 123.7 , 122.5 , 121.3 , 115.6 , 108.8 , 14.8 ; ir ( kbr )  
 3047 , 2925 1727 , 1452 , 1433 , 1344 , 1562 , 1601 , 1232 , 1082 , 714 cm ; hrms ( esi+ , qtof ) exact mass calcd for c21h15n4o2 [ m + h ] 355.1195 , found : 355.1180 .
yellow solid ( 72 mg , 71% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.28 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 216217 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.52 ( d , j = 8.4 hz , 1h ) , 
 8.43 ( d , j = 4.8 hz , 2h ) , 8.007.96 ( m , 2h ) , 
 7.837.81 ( m , 2h ) , 7.46 ( s , 1h ) , 7.21 ( dd , j = 8.8 , 2.0 hz , 1h ) , 6.94 ( t , j = 4.4 hz , 1h ) , 6.81 
 ( s , 1h ) , 2.48 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  167.9 , 158.2 , 157.6 , 134.6 , 134.2 , 132.6 , 132.2 , 127.8 , 
 126.5 , 125.3 , 124.2 , 121.1 , 117.0 , 115.8 , 109.5 , 21.6 ; ir ( kbr )  
 2920 , 1725,1425 1246 1100 718 cm ; hrms ( esi+ , 
 qtof ) exact mass calcd for c21h15n4o2 [ m + h ] 355.1195 , found : 355.1205 .
yellow solid ( 63 mg , 57% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.39 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 230231 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.58 ( d , j = 9.2 hz , 1h ) , 
 8.41 ( d , j = 4.8 hz , 2h ) , 7.97 ( dd , j = 5.4 , 3.0 hz , 2h ) , 7.82 ( dd , j = 5.4 , 3.0 hz , 
 2h ) , 7.13 ( d , j = 2.4 hz , 1h ) , 7.02 ( dd , j = 9.2 , 2.4 hz , 1h ) , 6.93 ( t , j = 4.8 
 hz , 1h ) , 6.82 ( s , 1h ) , 3.89 ( s , 3h ) ; c nmr ( 100 mhz , 
 cdcl3 )  167.6 , 157.9 , 157.3 , 155.7 , 134.3 , 132.3 , 
 130.6 , 128.1 , 125.5 , 123.9 , 117.1 , 116.7 , 114.2 , 109.4 , 103.0 , 55.7 ; 
 ir ( kbr )  2959 , 2927 , 2855 , 1727 , 1450 , 1421 , 1385 , 1211 , 1152 , 
 1081 , 810 , 717 cm ; hrms ( esi+ , qtof ) exact mass 
 calcd for c21h15n4o3 [ m + h ] 371.1144 , found : 371.1127 .
yellow solid ( 56 mg , 52% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.27 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 244 c ; h nmr ( 400 mhz , cdcl3 )  8.63 ( dd , j = 9.2 , 4.7 hz , 1h ) , 
 8.45 ( d , j = 4.8 hz , 2h ) , 7.98 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.83 ( dd , j = 5.6 , 3.2 hz , 
 2h ) , 7.33 ( dd , j = 8.8 , 2.6 hz , 1h ) , 7.13 ( dt , j = 9.2 , 2.6 hz , 1h ) , 6.98 ( t , j = 4.8 
 hz , 1h ) , 6.86 ( s , 1h ) ; f nmr ( 400 mhz , cdcl3 )  120.8 ; c nmr ( 100 mhz , cdcl3 )  106.2 ( d , jc 
f = 33 hz ) , 117.1 , 
 117.3 , 124.0 , 126.5 , 128.0 ( d , jc  f = 14 hz ) , 132.1 , 132.2 , 134.5 , 157.1 , 158.0 , 159.1 ( d , jc 
f = 288 hz ) , 167.5 ; ir ( kbr )  2924 , 2853 , 
 1787 , 1731 , 1447 , 1421 , 1202 , 1084 , 807 , 717 cm ; hrms ( esi+ , qtof ) exact mass calcd for c20h12n4o2f [ m + h ] 359.0944 , 
 found : 359.0928 .
yellow solid ( 76 mg , 68% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.40 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 237239 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.59 ( d , j = 9.2 hz , 1h ) , 
 8.46 ( d , j = 4.8 , 2h ) , 7.97 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.83 ( dd , j = 5.6 , 3.2 hz , 
 2h ) , 7.65 ( d , j = 2.4 hz , 1h ) , 7.35 ( dd , j = 8.8 , 2.0 hz , 1h ) , 7.00 ( t , j = 9.6 , 
 4.8 hz , 1h ) , 6.84 ( s , 1h ) ; c nmr ( 100 mhz , cdcl3 )  167.4 , 158.5 , 157.1 , 134.5 , 133.9 , 132.2 , 128.4 , 128.1 , 
 126.3 , 124.9 , 124.0 , 120.4 , 117.3 , 117.1 , 108.6 ; ir ( kbr )  
 3121 , 2926 , 1725 , 1442 , 1423 , 1386 , 1100 , 811 , 721 cm ; hrms ( esi+ , qtof ) exact mass calcd for c20h12n4o2cl [ m + h ] 375.0649 , 
 found : 375.0653 .
yellow solid ( 56 mg , 69% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.31 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 222 c ; h nmr ( 400 mhz , cdcl3 )  8.54 ( d , j = 9.0 hz , 1h ) , 8.46 
 ( d , j = 4.8 hz , 2h ) , 8.017.93 ( m , 2h ) , 7.877.79 
 ( m , 3h ) ,
7.47 ( dd , j = 9.0 , 2.0 hz , 1h ) , 7.00 ( t , j = 4.8 hz , 1h ) , 6.83 ( s , 1h ) ; c nmr ( 100 mhz , 
 cdcl3 )  167.4 , 158.1 , 157.1 , 134.5 , 134.3 , 132.2 , 
 129.0 , 127.5 , 126.3 , 124.0 , 123.5 , 117.5 , 117.3 , 115.7 , 108.5 ; ir 
 ( kbr )  3120 , 2924 , 1725 , 1566 , 1441 , 1421 , 1387 , 1099 , 811 , 
 720 cm ; hrms ( esi+ , qtof ) exact mass calcd 
 for c20h12n4o2br 
 [ m + h ] 419.0144 , found : 419.0147 .
yellow 
 solid ( 34 
 mg , 31% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 5:1 , v : v ) ; rf = 0.33 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 271272 c ; h nmr ( 400 mhz , cdcl3 )  8.71 ( d , j = 8.8 hz , 1h ) , 8.51 ( d , j = 4.8 hz , 2h ) , 
 8.04 ( s , 1h ) , 7.98 ( dd , j = 5.6 , 2.8 hz , 2h ) , 7.85 
 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.62 ( dd , j = 8.8 , 1.6 hz , 1h ) , 7.08 ( t , j = 4.8 hz , 1h ) , 6.96 
 ( s , 1h ) ; c nmr ( 100 mhz , cdcl3 )  167.1 , 
 158.3 , 156.8 , 137.3 , 134.6 , 132.1 , 129.9 , 127.5 , 127.2 , 126.1 , 124.1 , 
 119.8 , 118.0 , 116.7 , 108.8 , 105.9 ; ir ( kbr )  2923 , 2852 , 2223 , 
 1725 , 1576 , 1469 , 1422 , 1388 , 1101 , 1084 , 822 , 707 cm ; hrms ( esi+ , qtof ) exact mass calcd for c21h12n5o2 [ m + h ] 366.0991 , 
 found : 366.0981 .
yellow solid ( 49 mg , 46% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.29 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 182183 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.68 ( d , j = 8.4 hz , 1h ) , 
 8.40 ( d , j = 4.8 hz , 2h ) , 7.98 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.84 ( dd , j = 5.6 , 3.2 hz , 
 2h ) , 7.64 ( d , j = 8.0 hz , 1h ) , 7.42 ( dt , j = 7.2 , 1.2 hz , 1h ) , 7.327.28 ( m , 1h ) , 6.90 ( t , j = 4.8 hz , 1h ) , 2.30 ( s , 3h ) ; c nmr ( 100 mhz , 
 cdcl3 )  167.7 , 157.8 , 157.4 , 135.3 , 134.3 , 132.5 , 
 128.5 , 128.3 , 124.9 , 123.9 , 122.2 , 119.2 , 117.6 , 116.4 , 115.9 , 8.2 ; 
 ir ( kbr )  2923 , 1726 , 1562 , 1459 , 1426 , 1369 , 712 cm ; hrms ( esi+ , qtof ) exact mass calcd for c21h15n4o2 [ m + h ] 355.1195 , 
 found : 355.1217 .
yellow solid ( 73 mg , 72% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.41 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 174175 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.308.28 ( m , 1h ) , 7.917.88 

( dd , j = 5.6 , 3.2 hz , 2h ) , 7.827.80 ( m , 1h ) , 
 7.77 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.747.72 
 ( m , 1h ) , 7.60 ( dd , j = 8.4 , 1.2 hz , 1h ) , 7.537.51 
 ( m , 1h ) , 7.327.24 ( m , 2h ) , 7.15 ( ddd , j = 
 7.6 , 4.8 , 1.2 hz , 1h ) , 6.84 ( d , j = 0.8 hz , 1h ) ; c nmr ( 100 mhz , cdcl3 )  167.4 , 150.3 , 149.7 , 
 138.8 , 135.5 , 134.8 , 131.9 , 127.2 , 125.6 , 124.2 , 124.1 , 122.1 , 121.8 , 
 121.8 , 119.5 , 111.2 , 105.2 ; ir ( kbr )  3084 , 2925 , 1722 , 1583 , 
 1454 , 1371 , 736 , 712 , 883 , 608 cm ; hrms ( esi+ , 
 qtof ) exact mass calcd for c21h14n3o2 [ m + h ] 340.1086 , found : 340.1068 .
yellow solid ( 72 mg , 68% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.41 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 213 - 215 c ; h nmr ( 400 mhz , cdcl3 )  8.268.24 ( m , 1h ) , 7.89 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.797.74 ( m , 3h ) , 7.507.46 ( m , 
 3h ) , 7.127.10 ( m , 2h ) , 6.74 ( s , 1h ) , 2.47 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  167.4,150.5 , 149.6 , 138.7 , 
 135.0 , 134.7 , 133.8 , 132.0 , 131.1 , 125.6 , 125.4 , 124.4 , 124.2 , 121.9 , 
 121.4 , 119.2 , 110.9 , 21.7 ; ir ( kbr )  2924 , 1726 , 1471 , 1590 , 
 1432 , 1394 , 1337 , 1079 , 721 , 708 cm ; hrms ( esi+ , 
 qtof ) exact mass calcd for c22h16n3o2 [ m + h ] 354.1243 , found : 354.1226 .
yellow solid ( 86 mg , 78% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.27 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 199200 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.308.25 ( m , 1h ) , 7.90 ( dd , j = 5.6 , 2.8 hz , 2h ) , 7.827.74 ( m , 3h ) , 7.517.47 
 ( m , 2h ) , 7.16 ( d , j = 2.4 hz , 1h ) , 7.13 ( ddd , j = 7.2 , 4.8 , 0.8 hz , 1h ) , 6.95 ( dd , j = 
 9.2 , 2.8 hz , 1h ) , 6.7 ( s , 1h ) , 3.89 ( s , 3h ) ; c nmr ( 100 
 mhz , cdcl3 )  167.1 , 155.2 , 150.2 , 149.4 , 138.5 , 
 134.4 , 131.8 , 130.4 , 127.5 , 125.5 , 124.0 , 121.6 , 118.8 , 114.0 , 111.9 , 
 104.8 , 103.0 , 55.8 ; ir ( kbr )  2927 , 1726 , 1582 , 1482 , 1437 , 
 1213 , 1098 , 1079 , 789 , 721 , 709 cm ; hrms ( esi+ , 
 qtof ) exact mass calcd for c22h16n3o3 [ m + h ] 370.1192 , found : 370.1152 .
yellow solid ( 57 
 mg , 52% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 5:1 , v : v ) ; rf = 0.22 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 223225 c ; h nmr ( 400 mhz , cdcl3 )  8.398.37 
 ( m , 1h ) , 8.09 ( d , j = 1.6 hz , 1h ) , 7.91 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.85 ( dt , j = 7.6 , 
 1.6 hz , 1h ) , 7.81 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.64 
 ( d , j = 8.8 hz , 1h ) , 7.54 ( dd , j = 8.4 , 1.6 hz , 1h ) , 7.46 ( d , j = 8.0 hz , 1h ) , 7.257.23 
 ( m , 1h ) , 6.91 ( s , 1h ) ; c nmr ( 100 mhz , cdcl3 )  166.8 , 150.0 , 149.3 , 139.2 , 137.1 , 135.1 , 131.7 , 127.9 , 
 127.1 , 126.8 , 124.4 , 123.1 , 120.3 , 119.7 , 112.3 , 105.2 , 104.9 , 104.6 ; 
 ir ( kbr )  2924 , 2351 , 2218 , 1734 , 1471 , 1583 , 1398 , 1366 , 1082 , 
 883 , 802 , 717 cm ; hrms ( esi+ , qtof ) exact mass 
 calcd for c22h13n4o2 [ m + h ] 365.1039 , found : 365.1066 .
white 
 solid ( 34 
 mg , 31% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 3:1 , v : v ) ; rf = 0.16 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 185 c ; h 
 nmr ( 400 mhz , cdcl3 )  10.09 ( s , 1h ) , 8.388.34 
 ( m , 1h ) , 8.27 ( d , j = 1.2 hz , 1h ) , 7.927.79 
 ( m , 6h ) , 7.66 ( d , j = 8.8 hz , 1h ) , 7.50 ( d , j = 8.0 hz , 1h ) , 7.217.26 ( m , 1h ) , 6.99 ( s , 1h ) ; c nmr ( 100 mhz , cdcl3 )  192.4 , 166.9 , 149.9 , 
 149.5 , 139.1 , 138.8 , 134.9 , 131.8 , 131.2 , 127.5 , 126.9 , 126.6 , 124.4 , 
 124.1 , 122.9 , 119.8 , 111.9 , 106.3 ; ir ( kbr )  2927 , 2814 , 1732 , 
 1683 , 1588 , 1477 , 1392 , 1348 , 1303 , 1104 , 715 cm ; hrms ( esi+ , qtof ) m / z calcd 
 for c22h14n3o3 [ m 
 + h ] 368.1035 , found : 368.1028 .
yellow oil ( 20 mg , 27% yield ) ; purified 
 by column chromatography ( petroleum ether : etoac = 8:1 , v : v ) ; rf = 0.46 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; h nmr ( 400 mhz , cdcl3 )  
 7.79 ( dd , j = 3.2 , 5.6 hz , 2h ) , 7.71 ( dd , j = 3.2 , 5.6 hz , 2h ) , 7.677.62 ( m , 3h ) , 7.497.47 
 ( m , 1h ) , 7.297.26 ( m , 5h ) , 6.81 ( s , 1h ) ; c nmr 
 ( 100 mhz , cdcl3 )  168.3 , 166.5 , 135.8 , 134.6 , 134.5 , 
 132.3 , 131.4 , 129.3 , 128.4 , 127.4 , 125.6 , 125.1 , 123.8 , 123.3 , 121.3 , 
 114.8 , 109.0 ; ir ( kbr )  2923 , 1727 , 1683 , 1451 , 1379 , 1324 , 
 1079 , 701 ; hrms ( esi+ , qtof ) exact mass calcd for c23h15n2o3 [ m + h ] 367.1083 , found : 367.1079 .
yellow solid 
 ( 48 mg , 53% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 3:1 , v : v ) ; rf = 0.22 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 168 c ; h 
 nmr ( 400 mhz , cdcl3 )  8.298.27 ( m , 1h ) , 
 7.85 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.737.70 
 ( m , 3h ) , 7.65 ( dt , j = 8.0 , 2.0 hz , 1h ) , 7.607.54 
 ( m , 2h ) , 7.48 ( d , j = 8.0 hz , 1h ) , 7.447.38 
 ( m , 1h ) , 7.087.04 ( m , 1h ) ; c nmr ( 100 mhz , cdcl3 )  167.9 , 157.2 , 149.5 , 138.7 , 136.9 , 134.3 , 132.3 , 
 130.7 , 130.3 , 129.8 , 129.7 , 123.8 , 123.0 , 122.3 ; ir ( kbr )  
 2925 , 2854 , 1713 , 1469 , 1426 , 1382 , 1116 , 1099 , 1084 , 756 , 720 cm ; hrms ( esi+ , qtof ) exact mass calcd for c19h13n2o2 [ m + h ] 301.0977 , found : 301.0979 .
yellow solid 
 ( 45 mg , 48% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 5:1 , v : v ) ; rf = 0.41 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 178180 c , h nmr ( 400 mhz , cdcl3 )  8.278.25 
 ( m , 1h ) , 7.85 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.73 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.657.60 ( m , 2h ) , 7.45 ( d , j = 8.0 hz , 1h ) , 7.407.37 ( m , 1h ) , 7.22 ( s , 1h ) , 
 7.04 ( ddd , j = 7.6 , 4.8 , 1.2 hz , 1h ) , 2.47 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  168.1 , 157.1 , 149.4 , 
 140.0 , 136.9 , 135.8 , 134.2 , 132.4 , 130.9 , 130.7 , 130.5 , 129.6 , 123.8 , 
 122.9 , 122.1 , 22.2 ; ir ( kbr )  3057 , 2923 , 1719 , 1711 , 1467 , 
 1428 , 1379 , 1120 , 880 , 786 , 715 cm ; hrms ( esi+ , 
 qtof ) exact mass calcd for c20h15n2o2 [ m + h ] 315.1134 , found : 315.1112 .
yellow solid 
 ( 48 mg , 48% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 3:1 , v : v ) ; rf = 0.22 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 157158 c , h nmr ( 400 mhz , cdcl3 )  8.248.22 
 ( m , 1h ) , 7.85 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.73 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.67 ( d , j = 8.8 
 hz , 1h ) , 7.61 ( dt , j = 7.6 , 2 hz , 1h ) , 7.42 ( d , j = 8.0 hz , 1h ) , 7.11 ( dd , j = 8.8 , 2.8 
 hz , 1h ) , 7.047.00 ( m , 1h ) , 6.93 ( d , j = 2.8 
 hz , 1h ) , 3.89 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  167.6 , 160.2 , 156.6 , 149.1 , 136.5 , 133.9 , 132.0 , 131.3 , 
 130.8 , 130.6 , 123.5 , 122.3 , 121.5 , 115.4 , 55.5 ; ir ( kbr )  3002 , 
 1712 , 1375 , 1281 , 1466 , 1427 , 1113 , 875 , 788 , 716 cm ; hrms ( esi+ , qtof ) exact mass calcd for c20h15n2o3 [ m + h ] 331.1083 , 
 found : 331.1070 .
yellow solid ( 62 mg , 58% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.45 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 180181 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.288.27 ( m , 1h ) , 7.85 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.74 ( dd , j = 5.6 , 
 3.2 hz , 2h ) , 7.687.58 ( m , 3h ) , 7.46 ( d , j = 8.0 hz , 1h ) , 7.37 ( d , j = 2.0 hz , 1h ) , 7.097.02 
 ( m , 1h ) , 1.39 ( s , 9h ) ; c nmr ( 100 mhz , cdcl3 )  168.1 , 157.2 , 153.1 , 149.5 , 136.8 , 135.7 , 134.2 , 132.4 , 
 130.3 , 129.4 , 127.4 , 126.9 , 123.8 , 122.8 , 122.1 , 34.8 , 31.2 ; ir ( kbr ) 
  3047 , 2925 , 1727 , 1452 , 1433 , 1344 , 1601 , 1232 , 1082 , 887 , 
 816 , 741 , 714 cm ; hrms ( esi+ , qtof ) exact mass 
 calcd for c23h21n2o2 [ m + h ] 357.1603 , found : 357.1604 .
yellow solid ( 30 mg , 31% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.41 ( petroleum ether : etoac 
 = 2:1 , v : v ) ; mp 135 c ; h nmr ( 400 mhz , cdcl3 )  8.278.26 ( m , 1h ) , 7.86 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.74 ( dd , j = 5.6 , 3.2 hz , 
 2h ) , 7.70 ( d , j = 8.0 hz , 1h ) , 7.667.59 ( m , 
 2h ) , 7.47 ( d , 8.0 hz , 1h ) , 7.43 ( d , j = 1.6 hz , 1h ) , 
 7.06 ( ddd , j = 7.6 , 4.8 , 1.2 hz , 1h ) , 6.78 ( dd , j = 17.6 , 11.2 hz , 1h ) , 5.85 ( d , j = 17.6 
 hz , 1h ) , 5.37 ( d , j = 10.8 hz , 1h ) ; c nmr ( 100 mhz , cdcl3 )  167.9 , 156.8 , 149.5 , 139.3 , 
 137.7 , 136.9 , 135.6 , 134.3 , 132.3 , 130.8 , 130.1 , 128.2 , 127.5 , 123.8 , 
 122.9 , 122.3 , 116.1 ; ir ( kbr )  2927 , 2308 , 1717 , 1466 , 1424 , 
 1377 , 1116 , 719 , 715 cm ; hrms ( esi+ , qtof ) exact 
 mass calcd for c21h15n2o2 [ m + h ] 327.1134 , found : 327.1123 .
yellow solid 
 ( 49 mg , 51% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 5:1 , v : v ) ; rf = 0.27 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 196197 c ; h nmr ( 400 mhz , cdcl3 )  8.288.27 
 ( m , 1h ) , 7.86 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.767.70 
 ( m , 3h ) , 7.65 ( dt , j = 8.0 , 2.0 hz , 1h ) , 7.44 ( dt , j = 7.6 , 0.8 hz , 1h ) , 7.317.26 ( m , 1h ) , 7.17 ( dd , j = 8.8 , 2.4 hz , 1h ) , 7.107.06 ( m , 1h ) ; c nmr ( 100 mhz , cdcl3 )  167.5 , 164.0 , 161.6 , 156.4 , 
 149.5 , 137.1 , 134.5 , 132.2 , 123.9 , 122.9 , 122.4 , 117.9 , 117.6 , 116.9 , 
 116.8 ; f nmr ( 400 mhz , cdcl3 )  62.6 ; 
 ir ( kbr )  3069 , 2925 , 1720 , 1468 , 1424 , 1374 , 1269 , 1115 , 789 , 
 718 cm ; hrms ( esi+ , qtof ) exact mass calcd 
 for c19h12n2o2f 
 [ m + h ] 319.0883 , found : 319.0903 .
yellow solid ( 60 mg , 60% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.28 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 210 c ; h nmr ( 400 mhz , cdcl3 )  8.288.27 ( m , 1h ) , 7.85 ( dd , j = 5.2 , 2.8 hz , 2h ) , 7.75 ( dd , j = 5.2 , 2.8 hz , 
 2h ) , 7.687.62 ( m , 2h ) , 7.55 ( dd , j = 8.4 , 
 2.0 hz , 1h ) , 7.497.43 ( m , 2h ) , 7.10 ( ddd , j = 7.6 , 4.8 , 1.2 hz , 1h ) ; c nmr ( 100 mhz , cdcl3 )  167.2 , 155.9 , 149.3 , 136.9 , 136.8 , 134.8 , 134.1 , 131.8 , 
 131.4 , 130.6 , 130.2 , 129.6 , 123.6 , 122.6 , 122.3 ; ir ( kbr )  
 3085 , 1726 , 1712 , 1465 , 1420 , 1374 , 1118 , 1103 , 1082 , 717 , 709 cm ; hrms ( esi+ , qtof ) exact mass calcd for c19h12n2o2cl [ m + h ] 335.0587 , found : 335.0602 .
yellow solid ( 68 mg , 62% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.35 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 164 c ; h nmr ( 400 mhz , cdcl3 )  8.328.31 ( m , 1h ) , 7.887.83 ( m , 4h ) , 
 7.76 ( dd , j = 5.2 , 3.2 hz , 2h ) , 7.727.68 
 ( m , 2h ) , 7.50 ( d , j = 8.0 hz , 1h ) , 7.14 ( ddd , j = 7.6 , 4.8 , 0.8 hz , 1h ) ; c nmr ( 100 mhz , 
 cdcl3 )  167.5 , 155.9 , 149.7 , 142.1 , 137.2 , 134.5 , 
 132.1 , 131.6 , 131.3 , 130.5 , 127.7 , 126.6 , 124.0 , 123.7 , 123.1 , 123.1 ; f nmr ( 400 mhz , cdcl3 )  111.4 ; 
 ir ( kbr )  2922 , 1722 , 1371 , 1321 , 1115 , 1079 , 719 , 874 , 788 
 cm ; hrms ( esi+ , qtof ) exact mass calcd 
 for c20h12n2o2f3 [ m + h ] 369.0851 , found : 369.0820 .
yellow solid ( 42 mg , 39% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.35 ( petroleum ether : etoac 
 = 2:1 , v : v ) ; mp 184 c , h nmr ( 400 mhz , cdcl3 )  8.328.31 ( m , 1h ) , 8.24 ( dd , j = 8.0 , 1.6 hz , 1h ) , 8.10 ( d , j = 1.6 hz , 1h ) , 7.877.85 
 ( m , 2h ) , 7.82 ( d , j = 8.0 hz , 1h ) , 7.777.73 
 ( m , 2h ) , 7.68 ( dt , j = 7.6 , 1.6 hz , 1h ) , 7.547.49 
 ( m , 1h ) , 7.12 ( ddd , j = 7.6 , 4.8 , 1.2 hz , 1h ) , 3.96 
 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  167.6 , 
 166.0 , 156.2 , 149.7 , 142.8 , 137.1 , 134.4 , 132.2 , 131.8 , 131.4 , 130.9 , 
 130.8 , 130.2 , 123.9 , 123.2 , 122.9 , 52.7 ; ir ( kbr )  3070 , 2998 , 
 2949 , 1784 , 1717 , 1586 , 1422 , 1440 , 1288 , 1216 , 1114 , 765 , 718 cm ; hrms ( esi+ , qtof ) exact mass calcd for c21h15n2o4 [ m + h ] 359.1032 , found : 359.1002 .
yellow solid ( 27 mg , 28% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 3:1 , v : v ) ; rf = 0.29 ( petroleum ether : etoac 
 = 2:1 , v : v ) ; mp 217 c ; h nmr ( 400 mhz , cdcl3 )  10.11 ( s , 1h ) , 8.32 ( dd , j = 4.4 , 
 0.8 hz , 1h ) , 8.118.01 ( m , 1h ) , 7.947.90 ( m , 2h ) , 7.887.7.86 
 ( m , 2h ) , 7.787.68 ( m , 3h ) , 7.54 ( d , j = 8.0 
 hz , 1h ) , 7.167.13 ( m , 1h ) ; c nmr ( 100 mhz , cdcl3 )  190.9 , 167.5 , 156.0 , 149.7 , 144.1 , 143.0 , 137.2 , 
 134.5 , 132.1 , 131.9 , 131.6 , 130.9 , 130.3 , 124.0 , 123.3 , 123.2 ; ir 
 ( kbr )  3070 , 2818 , 2724 , 1715 , 1695 , 1465 , 1385 , 1111 , 1084 , 
 795 , 716 cm ; hrms ( esi+ , qtof ) exact mass calcd 
 for c20h13n2o3 [ m 
 + h ] 329.0926 , found : 329.0924 .
yellow solid 
 ( 42 mg , 45% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 5:1 , v : v ) ; rf = 0.35 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 164 c ; h 
 nmr ( 400 mhz , cdcl3 )  8.328.31 ( m , 1h ) , 
 7.84 ( dd , j = 5.2 , 2.0 hz , 2h ) , 7.72 ( dd , j = 5.2 , 2.0 hz , 2h ) , 7.62 ( dt , j = 7.6 , 
 2.8 hz , 1h ) , 7.55 ( s , 1h ) , 7.477.42 ( m , 1h ) , 7.387.35 
 ( m , 1h ) , 7.28 ( d , j = 8.0 hz , 1h ) , 7.07 ( ddd , j = 7.6 , 4.8 , 1.2 hz , 1h ) , 2.48 ( s , 3h ) ; c 
 nmr ( 100 mhz , cdcl3 )  167.8 , 157.0 , 149.3 , 139.6 , 
 138.3 , 136.5 , 133.9 , 132.1 , 131.2 , 130.1 , 129.7 , 126.9 , 123.5 , 122.6 , 
 122.0 , 21.3 ; ir ( kbr )  3077 , 2925 , 1726 , 1588 , 1471 , 1429 , 
 1380 , 1105 , 1084 , 892 , 826 , 721 cm ; hrms ( esi+ , 
 qtof ) exact mass calcd for c20h15n2o2 [ m + h ] 315.1134 , found : 315.1133 .
yellow solid ( 49 mg , 50% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 3:1 , v : v ) ; rf = 0.24 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 170 c ; h nmr ( 400 mhz , cdcl3 )  8.338.31 ( m , 1h ) , 7.84 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.72 ( dd , j = 5.6 , 3.2 hz , 
 2h ) , 7.63 ( dt , j = 8.0 , 2.0 hz , 1h ) , 7.44 ( dt , j = 8.0 , 1.2 hz , 1h ) , 7.31 ( d , j = 8.4 
 hz , 1h ) , 7.25 ( d , j = 3.2 hz , 1h ) , 7.107.07 
 ( m , 2h ) , 3.91(s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  168.2 , 160.4 , 156.9 , 149.5 , 139.9 , 136.9 , 134.2 , 132.3 , 
 131.4 , 123.8 , 122.9 , 122.5 , 122.3 , 116.0 , 115.1 , 55.9 ; ir ( kbr )  
 3014 , 2973 , 2934 , 1720 , 1561 , 1498 , 1459 , 1380 , 1295 , 1222 , 1031 , 
 796 , 719 cm ; hrms ( esi+ , qtof ) exact mass calcd 
 for c20h15n2o3 [ m 
 + h ] 331.1083 , found : 331.1054 .
yellow solid ( 41 mg , 44% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.35 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 182 c , h nmr ( 400 mhz , cdcl3 )  8.17 ( d , j = 4.0 hz , 1h ) , 7.78 
 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.68 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.577.49 ( m , 4h ) ,
7.477.41 ( m , 
 1h ) , 6.99 ( dd , j = 7.6 , 4.8 hz , 1h ) , 2.33 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  167.4 , 156.3 , 146.6 , 
 139.1 , 138.5 , 134.2 , 132.2 , 131.9 , 130.7 , 130.5 , 129.9 , 129.2 , 128.9 , 
 123.7 , 122.5 , 19.7 ; ir ( kbr )  2923 , 1710 , 1461 , 1446 , 1381 , 
 1121 , 1083 , 759 , 721 cm ; hrms ( esi+ , qtof ) exact 
 mass calcd for c20h15n2o2 [ m + h ] 315.1134 , found : 315.1117 .
yellow solid ( 60 mg , 54% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 8:1 , v : v ) ; rf = 0.48 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 203 c ; h nmr ( 400 mhz , cdcl3 )  8.168.15 ( m , 1h ) , 7.78 ( d , j = 5.2 , 3.2 hz , 2h ) , 7.67 ( d , j = 5.2 , 3.2 hz , 2h ) , 
 7.54 ( dd , j = 8.4 , 2.0 hz , 1h ) , 7.49 ( d , j = 8.0 hz , 1h ) , 7.43 ( d , j = 8.0 hz , 1h ) , 
 7.40 ( d , j = 2.0 hz , 1h ) , 6.97 ( dd , j = 7.6 , 4.8 hz , 1h ) , 2.35 ( s , 3h ) , 1.39 ( s , 9h ) ; c nmr 
 ( 100 mhz , cdcl3 )  167.6 , 156.4 , 152.4 , 146.6 , 138.4 , 
 136.1 , 134.1 , 132.2 , 132.1 , 130.3 , 130.0 , 126.8 , 126.1 , 123.6 , 122.3 , 
 35.0 , 31.5 ; ir ( kbr )  2965 , 2868 , 1715 , 1423 , 1373 , 1360 , 1122 , 
 1086 , 722 cm ; hrms ( esi+ , qtof ) exact mass calcd 
 for c24h23n2o2 [ m 
 + h ] 371.1760 , found : 371.1730 .
yellow solid ( 39 mg , 38% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 5:1 , v : v ) ; rf = 0.19 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 188 c ; h nmr ( 400 mhz , cdcl3 )  8.14 ( dd , j = 4.8 , 0.8 hz , 1h ) , 
 7.78 ( dd , j = 5.2 , 3.2 hz , 2h ) , 7.68 ( dd , j = 5.2 , 3.2 hz , 2h ) , 7.507.47 ( m , 1h ) , 7.42 ( d , j = 8.8 hz , 1h ) , 7.07 ( dd , j = 8.8 , 2.8 
 hz , 1h ) , 6.976.93 ( m , 2h ) , 3.88 ( s , 3h ) , 2.33 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  167.3 , 159.9 , 156.2 , 
 146.6 , 138.4 , 134.2 , 132.3 , 132.0 , 131.5 , 123.7 , 122.2 , 115.1 , 114.9 , 
 55.8 , 19.8 ; ir ( kbr )  3010 , 2937 , 1720 , 1617 , 1433 , 1377 , 1295 , 
 1272 , 1238 , 1085 , 716 cm ; hrms ( esi+ , qtof ) exact 
 mass calcd for c21h17n2o3 [ m + h ] 345.1239 , found : 345.1236 .
yellow solid ( 85 mg , 75% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 10:1 , v : v ) ; rf = 0.51 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 159160 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.18 ( dd , j = 4.4 , 1.2 
 hz , 1h ) , 7.807.78 ( m , 3h ) , 7.74 ( s , 1h ) , 7.71 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.65 ( d ,
j = 8.0 
 hz , 1h ) , 7.567.52 ( m , 1h ) , 7.03 ( dd , j = 
 7.6 , 4.8 hz , 1h ) , 2.34 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  166.9 , 155.1 , 146.9 , 142.7 , 138.8 , 134.5 , 132.3 , 
 131.8 , 131.6 , 131.4 , 131.3 , 127.3 , 125.8 , 123.9 , 123.1 , 122.4 , 19.5 ; f nmr ( 400 mhz , cdcl3 )  62.6 ; ir 
 ( kbr )  3068 , 2962 , 1716 , 1433 , 1376 , 1323 , 1211 , 1167 , 1143 ; 
 hrms ( esi+ , qtof ) exact mass calcd for c21h14n2o2f3 [ m + h ] 383.1007 , found : 383.0979 .
yellow solid 
 ( 51 mg , 54% yield ) , purified by column chromatography ( petroleum ether : etoac 
 = 8:1 , v : v ) ; rf = 0.41 
 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 234 c ; h 
 nmr ( 400 mhz , cdcl3 )  8.48 ( d , j = 4.8 hz , 2h ) , 8.34 ( d , j = 8.0 hz , 1h ) , 7.90 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.76 ( dd , j = 5.6 , 
 3.2 hz , 2h ) 7.42 ( d , j = 8.0 hz , 1h ) , 7.23 ( s , 1h ) , 
 7.00 ( t , j = 9.6 , 4.8 hz , 1h ) , 2.48 ( s , 3h ) ; c nmr ( 100 mhz , cdcl3 )  168.2 , 164.0 , 156.9 , 
 141.6 , 133.9 , 132.5 , 132.4 , 131.5 , 131.2 , 130.40 , 130.37 , 123.5 , 118.8 , 
 21.2 ; ir ( kbr )  2917 , 1719 , 1709 , 1566 , 1551 , 1410 , 1378 , 1112 , 
 1085 , 805 , 716 cm ; hrms ( esi+ , qtof ) exact mass 
 calcd for c19h14n3o2 [ m + h ] 316.1086 , found : 316.1066 .
yellow solid ( 45 mg , 43% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 8:1 , v : v ) ; rf = 0.41 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 248250 c , h nmr ( 400 mhz , 
 cdcl3 )  8.278.26 ( m , 1h ) , 8.19 ( s , 1h ) , 
 7.987.95 ( m , 3h ) , 7.87 ( dd , j = 5.6 , 3.2 
 hz , 2h ) , 7.76 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.69 ( td , j = 7.6 , 1.6 hz , 1h ) , 7.637.57 ( m , 3h ) , 7.107.07 
 ( m,1h ) ; c nmr ( 100 mhz , cdcl3 )  168.2 , 
 157.4 , 149.4 , 137.0 , 136.0 , 134.3 , 133.6 , 133.4 , 132.4 , 130.5 , 130.0 , 
 128.4 , 128.2 , 127.6 , 127.4 , 123.8 , 123.3 , 122.3 ; ir ( kbr )  
 3057 , 2924 , 1716 , 1587 , 1466 , 1425 , 1384 , 1110 , 869 , 749 , 711 cm ; hrms ( esi+ , qtof ) exact mass calcd for c23h15n2o2 [ m + h ] 351.1134 , found : 351.1142 .
yellow solid ( 94 mg , 97% yield ) , purified 
 by column chromatography ( petroleum ether : etoac = 8:1 , v : v ) ; rf = 0.46 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 299300 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.20 ( dd , j = 4.4 , 1.6 
 hz , 1h ) , 8.09 ( d , j = 8.0 hz , 2h ) , 8.02 ( dd , j = 5.6 , 3.2 hz , 2h ) , 7.89 ( d , j = 8.8 
 hz , 1h ) , 7.857.80 ( m , 3h ) , 7.727.68 ( m , 2h ) , 7.31 
 ( dd , j = 8.4 , 4.4 hz , 1h ) ; c nmr ( 100 
 mhz , cdcl3 )  169.3 , 148.1 , 145.5 , 135.8 , 133.7 , 
 133.4 , 131.1 , 130.4 , 129.2 , 128.0 , 127.8 , 127.3 , 127.1 , 126.5 , 123.5 , 
 121.6 ; ir ( kbr )  2925 , 2854 , 1727 , 1399 , 1382 , 1117 , 1086 , 
 844 , 726 , 717 cm ; hrms ( esi+ , qtof ) exact mass 
 calcd for c21h13n2o2 [ m + h ] 325.0977 , found : 325.0951 .
yellow solid ( 32 mg , 43% yield ) , 
 purified by column chromatography ( petroleum ether : etoac = 3:1 , v : v ) ; rf = 0.27 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 195 c ; h nmr ( 400 mhz , cdcl3 )  8.478.46 ( m , 1h ) , 8.08 ( d , j = 7.6 hz , 1h ) , 7.947.82 ( m , 3h ) , 7.787.72 ( m , 2h ) , 
 7.64 ( d , j = 8.4 hz , 1h ) , 7.53 ( d , j = 8.0 hz , 1h ) , 7.34 ( t , j = 7.6 hz , 1h ) , 7.277.19 
 ( m , 2 h ) , 7.06 ( s , 1 h ) ; c nmr ( 100 mhz , cdcl3 )  158.5 , 149.8 .
149.4 , 138.4 , 137.7 , 136.2 , 135.3 , 134.4 , 
 126.5 , 126.4 , 125.8 , 124.6 , 122.2 , 121.7 , 121.5 , 120.6 , 119.7 , 111.6 , 
 107.2 ; ir ( kbr )  2926 , 1745 , 1590 , 1470 , 1453 , 1331 , 1348 , 
 1187 , 748 , 584 ; hrms ( esi+ , qtof ) exact mass calcd for c20h14n3o3s [ m + h ] 376.0756 , found : 376.0748 .
yellow solid ( 36 mg , 32% yield ) , 
 purified by column chromatography ( petroleum ether : etoac = 3:1 , v : v ) ; rf = 0.27 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 235236 c ; h nmr ( 400 mhz , 
 cdcl3 )  8.58 ( d , j = 8.4 hz , 1h ) , 
 8.46 ( d , j = 4.4 hz , 2h ) , 8.19 ( d , j = 6.8 hz , 1h ) , 7.967.88 ( m , 3h ) , 7.71 ( d , j = 7.6 hz , 1h ) , 7.43 ( t , j = 7.6 hz , 1h ) , 7.30 ( t , j = 7.2 hz , 1h ) , 7.14 ( s , 1 h ) , 6.99 ( t , j = 4.8 hz , 1h ) ; c nmr ( 100 mhz , cdcl3 )  
 159.4 , 157.9 , 157.0 , 138.0 , 136.3 , 135.1 , 134.4 , 127.1 , 126.9 , 125.7 , 
 125.5 , 122.7 , 121.5 , 121.4 , 120.5 , 117.3 , 115.7 , 111.9 ; ir ( kbr ) : 
  2976 , 1751 , 1443 , 1424 , 1347 , 1186 , 755 ; hrms ( esi+ , qtof ) 
 exact mass calcd for c19h13n4o3s [ m + h ] 377.0708 , found : 376.0708 .
yellow solid ( 32 mg , 48% yelid ) , purified by column chromatography 
 ( petroleum ether : etoac = 3:1 , v : v ) ; rf = 0.22 ( petroleum ether : etoac = 3:1 , v : v ) ; mp 188 
 c ; h nmr ( 400 mhz , cdcl3 )  8.46 
 ( d , j = 4.4 hz , 1h ) , 8.05 ( d , j = 
 7.6 hz , 1 h ) , 7.89 ( t , j = 7.2 hz , 1h ) , 7.857.79 
 ( m , 3h ) , 7.677.58 ( m , 5 h ) , 7.147.11 ( m , 1 h ) ; c nmr ( 100 mhz , cdcl3 )  158.6 , 156.2 , 149.4 , 
 140.9 , 137.7 , 136.3 , 134.8 , 134.2 , 131.5 , 131.0 , 130.9 , 129.8 , 127.0 , 
 125.9 , 125.4 , 122.9 , 122.3 , 121.1 ; ir ( kbr )  3095 , 1748 , 1587 , 
 1471 , 1332 , 1311 , 1184 , 759 , 747 , 732 , 586 ; hrms ( esi+ , qtof ) exact 
 mass calcd for c18h13n2o3s [ m + h ] 337.0647 , found : 337.0638 .
yellow solid ( 12 mg , 22% yield ) ; purified 
 by column chromatography ( petroleum ether : etoac = 1:1 , v : v ) ; rf = 0.70 ( petroleum ether : etoac 
 = 3:1 , v : v ) ; mp 89 c ; h nmr ( 400 mhz , cdcl3 )  13.30 ( br , 1h ) , 8.79 ( d , j = 8.4 hz , 1h ) , 
 8.68 ( d , j = 4.4 hz , 1h ) , 8.04 ( d , j = 7.6 hz , 2h ) , 7.867.79 ( m , 2 h ) , 7.73 ( d , j = 7.6 hz , 1h ) , 7.527.46 ( m , 4h ) , 7.29 ( t , j = 6.4 hz , 1h ) , 7.29 ( t , j = 6.4 hz , 1h ) ; c nmr ( 100 mhz , cdcl3 )  165.5 , 158.3 , 147.3 , 138.1 , 
 137.9 , 135.7 , 131.5 , 130.3 , 128.8 , 128.6 , 127.4 , 125.6 , 123.6 , 123.0 , 
 122.0 , 121.9 ; ir ( kbr )  2960 , 2927 , 1666 , 1589 , 1475 , 1439 , 
 1323 , 1262 , 748 , 669 ; hrms ( esi+ , qtof ) exact mass calcd for 
 c18h15n2o [ m + h ] 275.1184 , found : 275.1183 .
compounds [ d]-4a and [ d2]-4a were synthesized 
 according to the literature procedure . under oxygen ,
cuoac ( 0.04 mmol , 4.9 mg ) , [ d]-4a ( 0.2 
 mmol , 31.2 mg ) , and phthalimide ( 0.24 mmol , 35.3 mg ) were dissolved 
 in toluene and o - dichlorobenzene ( 1:1 , 2 ml ) in an 
 oven - dried 25 ml schlenk tube .
the mixture was stirred at 150 c 
 for 4 h. the reaction was then stopped stirring , cooled down to room 
 temperature , and poured into naoh solution ( 10% , 10 ml ) . it was extracted 
 with etoac ( 3  20 ml ) .
the combined organic layers were dried 
 over na2so4 , filtered , and concentrated in vacuo . 

the residue was purified by column chromatography to give the corresponding 
 products [ d]-5a and 5a ( 28% yield ) .
the h nmr analysis showed that the ratio of 5a/[d]-5a is 2.1 . under oxygen , cuoac ( 0.04 mmol , 
 4.9 mg ) , [ d2]-4a ( 0.1 mmol , 15.7 mg ) , 4a ( 0.1 mmol , 15.5 
 mg ) , and phthalimide ( 0.24 mmol , 35.3 mg ) were dissolved in toluene 
 and o - dichlorobenzene ( 1:1 , 2 ml ) in an oven - dried 
 25 ml schlenk tube .
the mixture was stirred at 150 c for 4 h. 
 the reaction was then stopped stirring , cooled down to room temperature , 
 and poured into naoh solution ( 10% , 10 ml ) . it was extracted with 
 etoac ( 3  20 ml ) .
the combined organic layers were dried over 
 na2so4 , filtered , and concentrated in vacuo . 

the residue was purified by column chromatography to give the corresponding 
 products [ d]-5a and 5a ( 33% yield ) .
 a cu - catalyzed 
 aromatic c  h amidation with phthalimide under 
 oxygen as a terminal oxidant without using additional additives has 
 been achieved . 
 this reaction has the broad substrate scope and shows 
 moderate to good yields in most cases . 
 this method is complementary 
 to the previously reported metal - catalyzed c  h amination systems . 
Introduction
Results and Discussion
Conclusions
Experimental Section