23605-13-2Relevant articles and documents
INTRAMOLECULAR CYCLOADDITION REACTIONS OF VINYLKETENES. STEREO- AND REGIOSPECIFIC PREPARATION OF VINYLKETENES FROM α,β-UNSATURATED ACID CHLORIDES.
Kulkarni, Yashwant S.,Burbaum, Beverly W.,Snider, Barry B.
, p. 5619 - 5622 (1985)
Treatment of α,β-unsaturated acid chlorides 5, 6, 14, 17, and 18 with NEt3 in toluene at reflux generates, stereo- and regiospecifically, the vinylketene which undergoes a facile intramolecular cycloaddition.
Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates
Zhou, Yujing,Bandar, Jeffrey S.,Buchwald, Stephen L.
supporting information, p. 8126 - 8129 (2017/06/27)
The direct asymmetric copper hydride (CuH)-catalyzed coupling of α,β-unsaturated carboxylic acids to aryl alkenes to access chiral α-aryl dialkyl ketones is reported. A variety of substrate substitution patterns, sensitive functional groups, and heterocycles are tolerated in this reaction, which significantly expands the range of accessible products compared with existing hydroacylation methodology. Although mechanistic studies are ongoing, we propose that CuH-catalyzed silylation of unsaturated acids occurs to access a uniquely effective acyl electrophilic coupling partner.
Type III Intramolecular Cycloadditions of Vinylketenes
Snider, Barry B.,Allentoff, Alban J.,Kulkarni, Yashwant S.
, p. 5320 - 5328 (2007/10/02)
Treatment of trans α,β-unsaturated acid chlorides with Et3N in benzene at reflux gives a ca. 1:1 mixture of cis and trans α,β-unsaturated ketenes in excellent yield.If there is a second double bond in the side chain, the cis isomer undergoes a type III intramolecular cycloaddition to produce a bicyclohept-3-en-6-one and/or a bicyclohept-2-en-6-one in 30-50percent yield from the acid chloride.The effect of substituents on the stereochemistry and regiochemistry of the cycloaddition is described.
