期刊
CHEMICAL SCIENCE
卷 8, 期 2, 页码 1511-1524出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6sc04273b
关键词
-
资金
- NSF [CHE-1112397, CHE-030089]
- Robert A. Welch Foundation [AA-1280]
- ACS PRF [52801-ND4]
- NIH [GM 052964]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1546973] Funding Source: National Science Foundation
Chiral alpha,beta-unsaturated acylammonium salts are novel dienophiles enabling enantioselective Diels-Alderlactonization (DAL) organocascades leading to cis- and trans-fused, bicyclic gamma- and delta-lactones from readily prepared dienes, commodity acid chlorides, and a chiral isothiourea organocatalyst under mild conditions. We describe extensions of stereodivergent DAL organocascades to other racemic dienes bearing pendant secondary and tertiary alcohols, and application to a formal synthesis of (+)- dihydrocompactin is described. A combined experimental and computational investigation of unsaturated acylammonium salt formation and the entire DAL organocascade pathway provide a rationalization of the effect of Bronsted base additives and enabled a controllable, diastereodivergent DAL process leading to a full complement of possible stereoisomeric products. Evaluation of free energy and enthalpy barriers in conjunction with experimentally observed temperature effects revealed that the DAL is a rare case of an entropy-controlled diastereoselective process. NMR analysis of diene alcohol-Bronsted base interactions and computational studies provide a plausible explanation of observed stabilization of exo transition-state structures through hydrogen-bonding effects.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据