Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature

被引：11

作者：

Hernan-Gomez, Alberto ^{[1
]}

Orr, Samantha A. ^{[1
]}

Uzelac, Marina ^{[1
]}

Kennedy, Alan R. ^{[1
]}

Barroso, Santiago ^{[2
]}

Jusseau, Xavier ^{[2
]}

Lemaire, Sebastien ^{[2
]}

Farina, Vittorio ^{[2
]}

Hevia, Eva ^{[1
]}

机构：

[1] Univ Strathclyde, WestCHEM, Dept Pure & Appl Chem, 295 Cathedral St, Glasgow G1 1XL, Lanark, Scotland

[2] Janssen Pharmaceut, Pharmaceut Dev & Mfg Sci, Turnhoutseweg 30, B-2340 Beerse, Belgium

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 33期

关键词：

arylation; cooperative effects; transition-metal free; zinc; zincate; CROSS-COUPLING REACTIONS; ARYLZINC REAGENTS; GLYCOSIDES; ALKYL; HALIDES;

D O I：

10.1002/anie.201805758

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Pairing a range of bis(aryl) zinc reagents ZnAr2 with the stronger Lewis acidic [(ZnAr2F)] (Ar-F=C6F5), enables highly stereoselective cross-coupling between glycosyl bromides and ZnAr2 without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnAr2F acts as a non-coupling partner although its presence is crucial for the execution of the C(sp(2))-C(sp(3)) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition-metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases versus diarylzinc compounds (e.g. THF).

引用

页码：10630 / 10634

页数：5

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