Asymmetric synthesis of an atropisomeric β-carboline via regioselective intermolecular Rh(I)-catalyzed [2+2+2] cyclotrimerization

被引：0

作者：

Hughes, Riley R. ^{[1
]}

Battistoni, Lorenzo D. ^{[1
]}

Ciesla, Matthew J. ^{[1
]}

Bolton, Te'jandrio ^{[1
]}

Asher, Patrick M. ^{[1
]}

Irizarry, Giancarlo ^{[1
]}

Martinez, Alma de Jesus Antonio ^{[1
]}

Baker, Kristen M. ^{[1
]}

Mulcahy, Seann P. ^{[1
]}

机构：

[1] Providence Coll, Dept Chem & Biochem, 1 Cunningham Sq, Providence, RI 02918 USA

来源：

TETRAHEDRON LETTERS | 2024年 / 146卷

基金：

美国国家科学基金会; 美国国家卫生研究院;

关键词：

Asymmetric catalysis; Cyclotrimerization; Atropisomer; beta-carboline; CYCLOADDITION;

D O I：

10.1016/j.tetlet.2024.155187

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The rational design of atropisomeric small molecules is becoming increasingly common in chemical synthesis as a result of the unique advantages this property provides in drug discovery, asymmetric catalysis, and chiroptical activity. In this study, we designed a synthesis of a configurationally stable (3-carboline in six steps. Our synthesis made use of an innovative Grignard addition/elimination reaction that formed an yne-ynamide precursor that then reacted with ethyl cyanoformate in a rhodium(I)-catalyzed [2 + 2 + 2] cyclotrimerization reaction to give the atropisomeric (3-carboline in excellent yield, good enantioselectivity, and excellent regioselectivity. Extensive optimization of this transformation is described. Racemization kinetics experiments were also conducted on the individual atropisomers and their absolute configurations were determined by circular dichroism.

引用

页数：7

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