Cascade Grignard Addition: Propargyl Claisen Rearrangement for the Stereoselective Synthesis of α-Allene Quaternary Centers in Cyclohexanones

被引：0

作者：

Armendariz-Gonzalez, Estefania ^{[1
]}

Saputra, Adi ^{[1
]}

Mureka, Edward W. ^{[1
]}

Locicero, Cale M. ^{[1
]}

Womble, Gabrielle L. ^{[1
]}

Tan, Gloria ^{[1
]}

Watson, Abigail A. ^{[1
]}

Fronczek, Frank R. ^{[1
]}

Kartika, Rendy ^{[1
]}

机构：

[1] Louisiana State Univ, Dept Chem, 232 Choppin Hall, Baton Rouge, LA 70803 USA

来源：

ORGANIC LETTERS | 2025年 / 27卷 / 29期

基金：

美国国家科学基金会; 美国国家卫生研究院;

关键词：

ASYMMETRIC-SYNTHESIS; AZADIRACHTIN; CONSTRUCTION; REAGENTS; KETONES;

D O I：

10.1021/acs.orglett.5c02006

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We report a new method for the enantio- and diastereoselective synthesis of alpha-allene quaternary centers in fully substituted cyclohexanones at the alpha-positions. This reaction involves asymmetric 1,2-carbonyl addition to 2-O-propargyl enones using a mixture of Grignard reagents and the PMP-H8-BINOL ligand. The resulting magnesium alkoxide chelate intermediate then activated the propargyl vinyl ether moiety, thereby triggering a cascade propargyl Claisen rearrangement in a diastereoselective manner. The synthetic applications of this method in the context of complex molecules are also demonstrated.

引用

页码：7767 / 7772

页数：6

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