碳酸钾催化丙二烯酮与丙二酸二乙酯的1,4-加成反应研究：β,γ-不饱和烯酮和α-吡喃酮的可控选择性合成

Studies on K2CO3-catalyzed 1,4-addition of 1,2-allenic ketones with diethyl malonate: controlled selective synthesis of beta,gamma-unsaturated enones and alpha-pyrones.

作者信息

Ma Shengming, Yu Shichao, Yin Shaohu

机构信息

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P.R. China.

出版信息

J Org Chem. 2003 Nov 14;68(23):8996-9002. doi: 10.1021/jo034633i.

DOI:10.1021/jo034633i

PMID:14604373

Abstract

The K2CO3 (10 mol %)-catalyzed 1,4-addition reaction of diethyl malonate with various substituted 1,2-allenic ketones leading to polyfunctionalized beta,gamma-unsaturated enones 3 or 4 was studied. With 3-unsubstituted 1-substituted-1,2-allenyl ketones, the highly selective formation of beta,gamma-unsaturated enones 4 was observed; with 1,2-allenyl ketones bearing one or two 3-substituents in the allenyl group, only beta,gamma-unsaturated enones 3 with an unmigrated carbon-carbon double bond were produced; with 3-monosubstituted-1,2-allenyl ketones Z-beta,gamma-unsaturated enones 3 were formed with excellent stereoselectivity (E:Z > 96:4); with propadienyl ketones, mixtures of beta,gamma-unsaturated enones 3 and 4 were formed. alpha-Pyrone derivatives were synthesized via the K(2)CO(3)-catalyzed or -promoted reaction of 1,2-allenic ketones with diethyl malonate via a sequential Michael addition-carbon-carbon double bond migration-lactonization process.

摘要

研究了碳酸钾（10 mol%）催化丙二酸二乙酯与各种取代的1,2-联烯酮的1,4-加成反应，该反应生成多官能化的β,γ-不饱和烯酮3或4。对于3-未取代的1-取代-1,2-联烯基酮，观察到高度选择性地生成β,γ-不饱和烯酮4；对于在联烯基中带有一个或两个3-取代基的1,2-联烯基酮，仅生成具有未迁移碳-碳双键的β,γ-不饱和烯酮3；对于3-单取代的1,2-联烯基酮，以优异的立体选择性（E:Z > 96:4）生成Z-β,γ-不饱和烯酮3；对于丙二烯基酮，生成β,γ-不饱和烯酮3和4的混合物。α-吡喃酮衍生物是通过1,2-联烯基酮与丙二酸二乙酯在碳酸钾催化或促进下，经由连续的迈克尔加成-碳-碳双键迁移-内酯化过程合成的。