Synlett 2017; 28(08): 879-888
DOI: 10.1055/s-0036-1588139
synpacts
© Georg Thieme Verlag Stuttgart · New York

New Perspectives in Lithium Carbenoid Mediated Homologations

Vittorio Pace*
a  Department of Pharmaceutical Chemistry, University of Vienna, Althanstrasse 14, 1090 Vienna, Austria   Email: vittorio.pace@univie.ac.at
,
Laura Castoldi
a  Department of Pharmaceutical Chemistry, University of Vienna, Althanstrasse 14, 1090 Vienna, Austria   Email: vittorio.pace@univie.ac.at
,
Serena Monticelli
a  Department of Pharmaceutical Chemistry, University of Vienna, Althanstrasse 14, 1090 Vienna, Austria   Email: vittorio.pace@univie.ac.at
,
Marta Rui
a  Department of Pharmaceutical Chemistry, University of Vienna, Althanstrasse 14, 1090 Vienna, Austria   Email: vittorio.pace@univie.ac.at
b  Department of Drug Sciences, University of Pavia, Viale Taramelli 6, 27100, Pavia, Italy
,
Simona Collina
b  Department of Drug Sciences, University of Pavia, Viale Taramelli 6, 27100, Pavia, Italy
› Author Affiliations
Further Information

Publication History

Received: 11 December 2016

Accepted after revision: 09 January 2017

Publication Date:
01 February 2017 (online)

Dedicated to Professor Friedrich Hammerschmidt on the occasion of his retirement

Abstract

α-Functionalized organolithium reagents (e.g., LiCH2X) are versatile reagents for accomplishing homologations of carbon- and heteroatom-type electrophiles. The proper selection of the reaction conditions allows one to direct their intrinsic ambiphilicity towards the nucleophilic character. Herein, the homologation of various electrophiles ranging from Weinreb amides to isocyanates, carbonyl derivatives, and chalcogenides – with a particular focus on the chemoselectivity of the processes – is summarized.

1 Introduction

2 Homologation of Weinreb Amides

3 Homologation of Cyclic Ketones

4 Homologation of Isocyanates

5 Homologation of Disulfides and Diselenides

6 Conclusions

 
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