Decarboxylation-promoted Pd-catalyzed asymmetric propargylic [3+2] annulation for the enantioselective construction of a quaternary stereocenter in 2,3-dihydrofurans

被引：10
|
作者：
Li, Kun [1 ,2 ]
Zhu, Fu-Lin [2 ]
Liu, Zhen-Ting [2 ]
Tong, Jing [1 ]
Hu, Xiang-Ping [2 ]
机构：
[1] Liaoning Univ, Coll Chem, Shenyang 110036, Liaoning, Peoples R China
[2] Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Liaoning, Peoples R China
来源：
ORGANIC & BIOMOLECULAR CHEMISTRY | 2018年 / 16卷 / 05期
基金：
中国国家自然科学基金;
关键词：
TRANSITION-METAL-COMPLEXES; BETA-KETO-ESTERS; ORGANIC-SYNTHESIS; ALLYLIC ALKYLATION; CASCADE REACTIONS; CARBONATES; CYCLOADDITION; CYCLIZATION; DERIVATIVES; LIGANDS;
D O I：
10.1039/c7ob02778h
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The enantioselective construction of a quaternary stereocenter in 2,3-dihydrofuran frameworks has been realized via the palladium-catalyzed asymmetric [3 + 2] cycloaddition of tertiary propargylic carbonates with beta-ketoesters enabled by a chiral ferrocene/benzimidazole-based bidentate P, N-ligand. The reaction was significantly promoted by loss of CO2 to irreversibly form p-propargylpalladium or allenylpalladium intermediates. This protocol features a good tolerance of functional groups in both tertiary propargylic carbonates and beta-ketoesters, thereby delivering a variety of highly functionalized chiral 2,3-dihydrofurans bearing a quaternary stereocenter at the 2-position and an exocyclic double bond at the 3-position in good chemical yields and high enantioselectivities (up to 98% ee).
引用
收藏
页码：742 / 749
页数：8
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