Synlett 2019; 30(16): 1855-1866
DOI: 10.1055/s-0037-1611899
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© Georg Thieme Verlag Stuttgart · New York

Nitrosoalkenes: Underappreciated Reactive Intermediates for Formation of Carbon–Carbon Bonds

Steven M. Weinreb
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA   Email: smw@chem.psu.edu
› Author Affiliations
Further Information

Publication History

Received: 07 June 2019

Accepted after revision: 08 July 2019

Publication Date:
22 July 2019 (online)


This paper is dedicated to my longtime friend and colleague, Professor Philip DeShong, on the occasion of his 70th birthday.

Abstract

This Account describes studies carried out by my group during the past decade on both intra- and intermolecular conjugate additions of carbon nucleophiles to nitrosoalkenes. Using the Denmark protocol for the generation of nitrosoalkenes from α-chloro-O-silyloximes, a number of bridged and fused bicyclic ring systems can be prepared via the intramolecular version of this process. Intermolecular conjugate addition reactions of nitrosoalkenes with a wide variety of ester enolates as coupling partners can also be achieved efficiently using a similar procedure. Some stereochemical aspects of these nucleophilic additions have been studied with both acyclic and cyclic nitrosoalkenes. This methodology has been applied as key steps in synthetic approaches to some complex indole and Myrioneuron alkaloids.

1 Introduction

2 Conjugate Additions of Nitrosoalkenes

2.1 Background

2.2 Intramolecular Reactions

2.3 Intermolecular Reactions

2.4 Stereochemical Aspects

3 Applications to Natural Product Synthesis

3.1 Angustilodine and Related Alkaloids

3.2 Approach to Apparicine-Type Alkaloids

3.3 Myrioneurinol

4 Summary and Outlook

 
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