While the focus of this textbook is on organic reactions occuring in living cells, if you are a chemistry major, or are planning to take a standardized exam such as the MCAT, you will need to be familiar with a number of laboratory synthesis reactions. Here, we review the lab synthesis reactions covered in this text, which include most of the reactions typically covered in traditional organic texts. Click on the chapter/section number for direct links to the section where these reactions are introduced. NOTE : content below redirects to an older edition of the text, which differs from the current version in some content and organization. Section 8.5B: alcohols converted into good leaving groups Section 9.1B : Williamson ether synthesis alkyl halide must be methyl or primary to avoid competing elimination Section 11.4B: cyclic acetal ‘protects’ ketone/aldehyde group – stable to bases/nucleophiles deprotect with aqueous acid Section 12.2D: activates carboxylic acids acetic anhydride is a good acetyl group donor (activated acetic acid) adds acetyl group to acohols, amines Section 13.6A goes through enamine intermediate haloform reaction – also works with Br 2 , I 2 Section 13.6B Wittig reaction Section 13.6C Section 13.6D Grignard reagent – carbon nucleophile No acidic protons can be present (it’s a strong base) Can also use R-Cl Grignards add to esters, acid chlorides twice organolithium – similar to Grignard Gilman reagent Gilman reagent will react with alkyl, vinyl halides as well as carbonyls Gilman reagent will add once to acid chlorides to make a ketone Section 14.2B nucleophilic aromatic substitution Section 14.3A Hoffman elimination - least substituted alkene produced Cope elimination Section 15.2B Section 15.2D anti-Markovnikov addition of water to alkene. Notice syn addition! method to protect alcohol – remove with H 3 O + another alcohol protecting group: remove with F - ion Section 15.6A: watch out for the possibility of carbocation rearrangements! watch out for the possibility of carbocation rearrangements! ortho-para directing vs. meta-directing groups Section 15.7A: Markovnikov addition of water without possibility of carbocation shifting Section 15.7C: pinacol rearrangement Hoffman rearrangement Section 15.10: Diels-Alder: cis/trans stereoselectivity bicyclic Diels-Alder product - no stereoselectivity Cope rearrangement Claisen rearrangement Section 16.11B: Section 16.13A: reduces aldehydes/ketones, but not carboxylic acid derivatives reduces aldehydes, ketones, carboxylic acid derivatives can reduce ester/amide to aldehyde (LiAlH 4 can't do this) Section 16.13B: alkynes, aldehyde, ketones, nitro groups also reduced by H 2 /Pt (but not acid derivatives!) alkyne to cis-alkene alkyne to trans-alkene Section 16.13C: Section 16.13D: primary alcohol to acid secondary alcohol to ketone oxidation at the benzylic position Swern oxidation abbreviated PCC cis diols cleaved, not trans KMnO 4 also oxidizes primary alcohols and aldehydes to acids Section 17.2B: radical halogenation is regiospecific – depends on stablity of radical intermediate NBS can be source of Br in radical halogenation reactions regiospecificity: benzylic / allylic Organic Chemistry With a Biological Emphasis by Tim Soderberg (University of Minnesota, Morris)