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Purchase, R.; Sainsbury, M., Science of Synthesis, (2009) 40, 382.
Among a variety of approches to allylic amines that employ [3,3]-sigmatropic rearrangements of such starting materials as allylic carbamates,[93] isoureas,[94] cyanates,[95–97] thioimidates,[98,99] sulfamates,[100] phosphorimidates,[101,102] and others,[103] aza-oxa-Cope conversions of acetimidates into acetamides (see Section 40.1.3.1.4.2) may be the most adaptable as, not only are the starting materials easy to prepare, the rearrangements proceed with predictable stereochemical control. In typical examples, allylic trichloroacetimidates 99 undergo irreversable aza-Claisen rearrangements to afford trichloroacetamides 100 that may then be hydrolyzed to give allylic amines 101 (Scheme 28).[104,105]
Meeeee 88 Mee Meeeeeeeeeeee ee Meeeeee Meeeeeeeeeeeeeeeeeeee[88,888]
Mee eee eeee ee eeee eeeeeeeee ee eee eeeeeeee eeeee ee eee Meeeeee eeeeeeeeeeeee, eee ee eeee eeeeeeeeee eeee e eee-eeeeee eeeee-eeee eeeeeeeeee eeeee eee eeeeeee; ee ee eeeeeeeee ee eeee eee/ee eeeeeee eee eee ee eeeeeeeee. Mee eeeeeeeeeee [8,8]-eeeeeeeeeee eeeeee ee eee eeeeeee eeeeeee e eeeee [8,8] eeeeeeeeeeeee ee eee eeeeeee eeee eeee eeeeeeeeeeeeee eeeeeee eeee eeee eeeeeeeee ee eeeeeeeeeeeee eeeee eeeee; eeeeeeee, eee eee ee eeeeee eeeeeeeee eeeeeeeee ee eeeeeeeee eee ee eeee ee eeeeeeeee eeeeeeeeeeeeeeeeee eeee eeeeeee Meeeeee eeeeeeeeeeeeee eeee eee eeeeeeee eeeeeeeee eee eeeeeee. Mee eeeeee ee eee ee eeeeeeeeee eee eee eee eeeee eee ee eeeeee ee eeeeeeee eeeeeeeeeeee ee eee eeeeeeeeeeee ee eeeeeeeeeeee, eeeee eeeee, eeeeeeee, eeeee eeeeee, eee eeeeeeeeeee, eeeee eeee eeeeee. Me e eeeeeeee eeee (Meeeee 88) eee eeeeeeeeeeeeeeeeeeee 888 ee eeeeeeee ee eeeeeeeee eeee eee eeeeeee eeeeee 888 eeee ee ee eeeeee ee eeeeee ee 888°M.[888] Me eeee eeeeeeeeee eeeeeeee e eeee eeeeeeeeeee eeeee eeeee ee eeeeee ee eeeeeeee ee eeeeeeeeeeee (ee 888°M), ee eeeeee eeee eee ee eee ee ee eeeeeeee eeeeee eeeeeeeeeee ee eee eeeeee-eeeeeee eeeeee eeee eeeeee eee eeeeeeeeee eeeee 888. Meeeeee, eeee eee eee a eeeeeeeeeeee eee ee e eeeeeee eeee eee eeeeeeeeee eeeeee ee eeeee eee eeee eeeeee eee eeeeeeee; ee e eeeeee e eeeeeee ee eeeeeee eee eeee ee eeeeeeee ee eee eeeeeeeeeeeee ee eee eeeeeeeeeee 888 eeeee e 88:88 eeeeeee ee eee M/M-eeeeeee 888M/888M ee eeeeeeee (Meeeee 88).
Meeeee 88 Meeeeeeeeeeee ee eee Meeeeeeeeeeeeeeeeeee ee Meeeeeee[888]
Meee eeeeeeeee, eeeeeee, eeeeee eeeeeeeeeeeeee eeeeeee ee eee ee eee eeeee eeeeeeeeee ee eee Meeeeee eeeeeeeeeeeee. Mee eeeeeee, eeeeeeeee eeee eeeeee a-eeeee eeeee 888 eee ee eeeeeeee eeee eeeeee eeeeeeeeeeeeeeeeeeeee 888, eeeee eee eeeeee eeeeeeeee ee eee eeeeeeeee eeeeee eeeeeeeeeeeeeeeeeee 888 eee eeeeeeeee ee eeeeeeeee eeeeeeee (Meeeee 88).[888] Me e eeeeeee eeeeee, eee eeeeeeeeeee eeeeee ee eee Meeeeee eeeeeeeeeeeee eee eeee eeeee eeee eeeee ee eeeeeeeeeeee eeeeeeeeee eee ee eeeeeeeeee ee eeeeee eee eeeeeeeeeee eeeeee eeeeeeeeeeeeeeeeeee, eee eeee eeeeeeeee eeeeeee ee eeeeeeeeeeeeeeeeeeeee eeee ee 888M eee 888M, eeee eee eeee eeeeeeeeeeeee ee eee eeeeeee eeee, eeee eee eeeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeeeeeeeeeee (Meeeee 88).[888]
Meeeee 88 Meeeeeeee ee Meeeeeeee Meee a-Meeee Meeee eee eee Meeeeeeeee ee Meeeeeeeeee eeee eee Meeeeee Meeeeeeeeeeeee ee Meeeeee Meeeeeeeeeeeeeeeeeeee eeee Meeeeeeee Meeeee-Meee Meeeeeee[888,888]
Mee eeeeeeee eeeeeeeee eee eee Meeeeee eeeeeeeeeeeee eee eeeeeee eeeeeeee eeee eeeeeee eeeeeeee ee eeeeeeeee eeee eeeeeeeeeeeeeeeeeeeee; eeee eeeeeeeee eee eeeeeeee eeeeeeeee eeeeeeeeeee eeeeee eee eeeeeeeeeeeee eeee ee eeeeeee eee, eeeee e eeee ee eeee eee eeeeeeee ee eee eeeeeee eeeeeee. M eeee eeeeeee ee eeeee eee ee eeee eee eeee eeeeee eeeeeee eee eeeeee eeeee eeeeeeee (ee ee eeeeeee eeeeeee eeee ee eeeeeeeeeeeeeee) ee 8,8-eeeeeeeeeeee[8.8.8]eeeee-8-eee, eeeeee eeeeeeeeeeeee[888] ee ee eeeeee,[888–888] eee eeeeeeee eeeeeeee. Meee eeee eeeeeee eeeeeeeeee eee eeeeeeee ee, eee eeeeeee, eeee eeeeeeee eeeeeeee eee eee eeeeeeeeee 88-eeeee-8 ee eeeee ee eeeeeeee eeeeeeeee eeeeeee eee, eeee ee, eeee eeeeeeee eeeee eee eeeee ee eeeeeeeee ee eeeeeeee eee eeeeeeeee ee eee eeeeeeeeeeeeeeeeeeee.[888] Me eeee eeeeeeeee eeeeeeeeeeeeeeeeeeeee, eeeeee eeee eeeeeeeeeeeeeeeee, eee eeee eeee eeeeeeeee ee Meeeeee eeeeeeeeeeeeee ee eeee eee eeeeeee eee eeeeeeee eeee; eeeeeee eee eeeeeeee eeeeeeee eee eeeee eeeeeeeeeee, eeeeeeeeeeeeeeeeeeeee, ee e eee. Me eeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeeee ee eeeeeeee eeee eeeeee eeeeeeee, ee eee eeeeeeee ee eeeeeeee eeeeeeeee eee eeeeeeeeeeeee, ee eeeeeeee eee eeeee eeeeeee, eeeee ee eeee eeeeeeee eeee eee eeeeeee eeeeeee ee eeee eeeee 8,8-eeeeeeeeeeee[8.8.8]eeeee-8-eee ee eee eeee.[888] Meeeee 88 eeeee e eee eeeeeeeeeeeeee eeeeeeee ee eee Meeeeee eeeeeeeee ee eeeee eeeeee eeeeeeeee- ee eeeeeeeeeeeeeeeeeeeee eee eeee.[888–888]
Meeeee 88 Meee Meeeeeeeeeeeee Meeeeeee ee Meeeeee Meeeeeeeeeeeee ee Meeeeeeee- ee Meeeeeeeeeeeeeeeeeeee[888–888]
Meee eeeeeeeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeeeeee eee eeeeeee eeee eee eeeeeee eeeeeeeee ee eeee eee eeeeeeee ee eeeeee ee eeeeeeeee eeeeeeeee eee ee eeeeeeee. Mee eeeeeee, ee eee Meeeeee eeeeeeeeeeeee ee eee eeeeeeeeeee 888 eee eeeeeee eeeee ee eee eeeeeeeeeeeee eeeeeeeee 888 ee 88% (eeee eee eeeeeee eeeeeee), eeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeeeee eeee ee eeeeeeeee ee 88% (Meeeee 88).[888] Meee eeeeeee eeeeeeeeeeee ee eeeee eee M=M eeee ee eeeeeeee ee e eeeeeeeeee eeee eee eee eeeeeeee eeeeeeeee, eee eeeeeeee ee e eeeee eeeeeeeeee eeeee ee eee eeeeeeee, eee ee eeeeeeeeeee eeeeee eeeeee eeeeeeeeee eeeee ee eeeeeeee ee eeeee ee eeeeeeee eee eeeee eeeeeeeee eeeeeeeeeeee eeeee ee eee eeeeeeeeee eeeeee eeee ee eeeee eee eeeeeeeeeeeee ee eeeee. Meeeeee, ee eee eeeeeeeeeeee eeeeee eeeee ee eeeeeee eeeeeeeeeeeee ee eee eeeeee eeeeeeeeeeee eee eeeeee ee eeeee eee [8,8]-eeeeeeeeeee eeeeee, eee eeeeeeee ee ee eeeeee eeeee eeeeeeeee ee eeeeeeee eee eeeeeeeeee ee eeeeeeee eeee-eeeeeeeee eeeeeeeeee ee eee eeeeeeeee, ee eeeeeeeeeee ee eee eeeeee eeee ee eeeeeeeeeee eeeee ee Meeeee 88, eeeee eee eeeeeeeeeeee eeeeeeeeeee 888 ee eeeeeeee ee eeeeeee eeeeeeeeeeeee ee eee eeeeeeeee 888 eeee eee eeeeeee eeeee eeeeeeeee eeeeeeeee.[888,888]
Meeeee 88 Meeeee ee Meeeeeeee Meeeeeeee ee eee Meeeee ee Meeeeee Meeeeee Meeeeeeeeeeee Meeeeeeee[888,888]
Meeeeeeee eee eeeeeeeeee eeee ee eeeeeee Meeeeee eeeeeeeeeeeeee eee eeee eeeeeeee eee eeeeeeeeeee ee Meeeee 88.[888,888] Meeeee, eeeee ee eeeeeeeee ee eee eeeeeee ee eeeeeee eee eeeeeeeee eeeeeeeee; eeee, eeee eee M-eeeeeeeee eeeeeeeeeeeeeeee 888 (eeeeeeee eeee eee eeeeeeeeeeeee eeeeeee ee 88% eeeee eeeee eeeeee eeeeeee eee eeeeeeeeeeeeeeeeeeeee) ee eeeeeeeeee ee eeeeeee ee 888°M ee e-eeeeee (Meeeee M) eee eeee/eee eeeee ee eee eeeeeeeeeeeee eeeeeeeeee 888M/888M ee 88:88; eeeeeee, ee eee eeeeeeee ee e eeeeeeeee eeeeeeee (Meeeee M) eeee ee eeeeeee ee eeee eee eeee-eeeeee eeeeeee eee eeeeeeeee eeeeeee. Meee ee eeeeeeee ee eeeeeeeeeeeeeeee eee eeeeee eeeeeee eee eeeeeeee eeeeeeeeeee ee eee eee eeeeeeeee eeeeeeee eeeee ee eee eeeeeeeeee eeeeeeeeee eeeee 888 eee eeeeeee eeeeeeee eeeeee eee eeee-eeeeeee 888M (Meeeee 88).[888] Meeeeeeee 888M eee ee eeeeeeeee eeee eee eeee 888 ee eeeeeeeee eeeeeeeeeee ee eee eeeee eeee. Meeeeeeeee eeeeeee ee eeee eee eeeeeeeeeeeeeeeeee eee eeee-eeeeeeeeeeeeee eeeeee eeeeeee eee a,B-eeeeeee eeee 888. Me eeeeee ee eeeee eeee eeee eeeee-eeeeeeeee eeeeeeeee eee ee eeee eeeeeeeee eeee eeeee eeeeeeeee eeeeeeee eeeeeeeeeeee.[888]
Meeeee 88 Meeeeeee ee Meeeeee Meeeeeeeeeeeee Meeeeeeee ee Meeeeee, Meeeeeeee, ee Meeeeeeee Meeeeeeee[888,888,888,888]
M eeeee eeeeeee ee eeee eeee ee eeeeeeee ee eee eeeeeeeeeeee ee eeeeeeeee, eeee ee eee eeeeeeeeee eeeeeeeee–eeeeee eeeeeee 888 [(M)-MMM-Me] eee eeeeeee eeeeeeeee,[888–888] eeeee eee eeee ee eeeeee eeeeeeeeeeeeeeeeee eeee eeeeeeeeeeeeeeeeeeee–eeeeeeeeeeeeeeeeee eeeeeeeeeeeeee. Mee eeee eeeeeee ee eeeeeeeeeee ee Meeeee 88, eeeee eee eeeeeeeeeeeeeeeeeeee 888 ee eeeeeeeee eeee eee eeeeee eeeeeeeeeeeeeeeeee 888 eeeee eee eeeeeeeeee eeeeeeee 888 (Meeeee 88).[888]
Meeeee 88 Meeeeeeee ee 8,8,8-Meeeeeeee-M-[(8M)-8-eeeeee-8-eeeeeeeeee]eeeeeeeee eeee (8M)-8-Meeeeeeee-8-eeee 8,8,8-Meeeeeeeeeeeeeeeeeee[888]
Meeeeeeeeeee Meeeeeeee
8,8,8-Meeeeeeee-M-{(8M)-8-[(8M)-8,8-eeeeeeee-8,8-eeeeeeee-8-ee]-8-eeeeee-8-eeeeeeeeeeeee-8-eeee}eeeeeeeee (888):[888]
MMM (88.8 eM, 88.8 eeee) eee eeeee ee e eeee ee (8M)-8-{8-[(8M)-8,8-eeeeeeee-8,8-eeeeeeee-8-ee]-8-eeeeeeeeeeeeee-8-eeeeeeeee}eeeeeee (88.8 e, 88.8 eeee) ee eee MM8Me8 (888 eM) eeeeeeeeee eeeeee ee −88°M, eee Me8MMM (8.88 eM, 88.8 eeee) eee eeee eeeee eeeeeeee ee eee eeeeeee eeee e eeeeee ee 88 eee. Mee eeeeeee, eeeee ee −88°M, eee eeeeeee eee 8 e, eeeeee eee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee eee. ee MM8Me (888 eM). Mee eeeeeeeee eeeeeee eee eeeeeeeee eeeeeee eeeee eeee MM8Me8 eee eee eeeeeeee eeeeeeee eeee eeeee (Me8MM8) eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeeeee ee Me8M eee eee eeee eee eeee eeeeee eeeeeee e eeeee eeeeee eeeeee eeee eeeee Me8MM8 eee eeeeee eee 88. Mee eeeeeee eee eeeeeee eeee eee eeeeeeee ee eeeeee eee eeeeeee 888 ee e eeeee eeeeee eee.
Meeeeeee M8MM8 (8.8 e) eee eeeee ee e eeee ee eee eeeee eeeeeee 888 ee e-eeeeee (888 eM) eee eee eeeeeee eee eeeeee, eeee eeeeeeee eeeeeeee, ee eeeeee eee 88 e. Meeee eeee eeeeeeeee, eee eeeeeee eee eeeeee ee ee eee eeeeeeee eeeeeee Meeee-Mee, eee eee eeeee ee eee eee eee eeeeee eeee eeeeeee. Mee eeeeeeee eeeeeeeee eeee eeeeeeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeee 8:88 ee 8:8) ee eeeeee eeeeeeeee eeeeeeee; eeeee: 88.8 e (88% eee eee eeeee).
References
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 88e, 8888.
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