Confined acids catalyze asymmetric single aldolizations of acetaldehyde enolates

被引：71

作者：

Schreyer, Lucas ^{[1
]}

Kaib, Philip S. J. ^{[1
]}

Wakchaure, Vijay N. ^{[1
]}

Obradors, Carla ^{[1
]}

Properzi, Roberta ^{[1
]}

Lee, Sunggi ^{[1
]}

List, Benjamin ^{[1
]}

机构：

[1] Max Planck Inst Kohlenforsch, Kaiser Wilhelm Pl 1, D-45470 Mulheim, Germany

来源：

SCIENCE | 2018年 / 362卷 / 6411期

基金：

欧洲研究理事会;

关键词：

CROSSED-ALDOL REACTION; ALDEHYDES; METHYL;

D O I：

10.1126/science.aau0817

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert-butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.

引用

页码：216 / 219

页数：4

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