Acetal Substitution Reactions: Stereoelectronic Effects, Conformational Analysis, Reactivity vs Selectivity, and Neighboring-Group Participation

被引：6
作者：
Chun, Yuge [1 ]
Luu, Khoi B. [1 ]
Woerpel, K. A. [1 ]
机构：
[1] NYU, Dept Chem, 100 Washington Sq East, New York, NY 10003 USA
来源：
SYNLETT | 2024年 / 35卷 / 15期
基金：
美国国家卫生研究院;
关键词：
acetals; oxocarbenium ion; stereochemical model; neighboring-group effects; addition to carbonyl compounds; enolates; MOLECULAR MECHANICAL INVESTIGATIONS; HIGHLY STEREOSELECTIVE REACTIONS; OXOCARBENIUM ION INTERMEDIATE; C-GLYCOSYLATION REACTIONS; SINGLE-ELECTRON-TRANSFER; ALPHA-ALKOXY KETONES; NUCLEOPHILIC ADDITIONS; AMBIDENT REACTIVITY; GAMMA-LACTOLS; DIVERGENT DIASTEREOSELECTIVITY;
D O I：
10.1055/s-0042-1751541
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Acetal substitution reactions can proceed by a number of mechanisms, but oxocarbenium ion intermediates are involved in many of these reactions. Our research has focused on understanding the con-formational preferences, structures, and reactions of these intermediates. This account summarizes our observations that electrostatic effects play a significant role in defining the preferred conformations, and that torsional effects determine how those intermediates react. Neigh-boring-group effects are not as straightforward as they might seem, considering that oxocarbenium ion intermediates are in equilibrium with structures that involve stabilization by a nearby substituent.
引用
收藏
页码：1763 / 1787
页数：25
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