The Aldol-Tishchenko Reaction of Butanone, Cyclobutanone and a 3-Pentanone Derived Sulfinylimine and DFT Calculations of the Stereo-determining Step

被引：1

作者：

Alcock, Emma ^{[1
]}

Mackey, Pamela ^{[1
]}

Turlik, Aneta ^{[2
]}

Bhatt, Khushi ^{[2
]}

Light, Mark E. ^{[3
]}

Houk, Kendall N. ^{[2
]}

McGlacken, Gerard P. ^{[1
]}

机构：

[1] Univ Coll Cork, Sch Chem & Analyt & Biol Res Facil, Cork T12 YN60, Ireland

[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[3] Univ Southampton, Chem Dept, Univ Rd, Southampton SO17 1BJ, England

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2023年 / 29卷 / 22期

基金：

美国国家科学基金会;

关键词：

1; 3-amino alcohol; DFT; diastereoselective; stereochemistry; ACYCLIC AMINO-ALCOHOLS; C-H AMINATION; ASYMMETRIC-SYNTHESIS; STEREOSELECTIVE-SYNTHESIS; 1,3-AMINO ALCOHOL; BETA-AMINO; DERIVATIVES; SYN; SYN-1,3-AMINO; ANTI-1,3-AMINOALCOHOLS;

D O I：

10.1002/chem.202203029

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein, we present a highly diastereoselective method to furnish acyclic 3-amino-1,5-diol derivatives using a tandem double-aldol-Tishchenko protocol (dr up to >99 : 1) using a butanone derived sulfinylimine. In most cases only 1 diastereomer predominates, from a possible 16. The reaction is also regioselective. In addition, the highly challenging cyclobutanone and 3-pentanone derivatives are also amenable to a double-aldol-Tishchenko reaction, although the dr values are modest. Despite that, clean single diastereomers can be isolated, which should prove very useful in medicinal chemistry and other areas. Detailed DFT calculations support the observed stereoselectivities in all cases, providing a rationale for the excellent dr values in the butanone series and the moderate values for the 3-pentanone class.

引用

页数：7