A Complementary Toolbox of Iterative Methods for the Stereo­selective Synthesis of Heteroatom-Rich Motives from C1-Building Blocks

Sujenth Kirupakaran; Hans-Gert Korth; Christoph Hirschhäuser

doi:10.1055/s-0036-1591996

Synthesis, Table of Contents

Synthesis 2018; 50(12): 2307-2322
DOI: 10.1055/s-0036-1591996

short review

A Complementary Toolbox of Iterative Methods for the Stereoselective Synthesis of Heteroatom-Rich Motives from C₁-Building Blocks

Sujenth Kirupakaran

University Duisburg-Essen, Universitätsstraße 7, 45117 Essen, Germany Email: Christoph.Hirschhaeuser@uni-due.de

,

Hans-Gert Korth

University Duisburg-Essen, Universitätsstraße 7, 45117 Essen, Germany Email: Christoph.Hirschhaeuser@uni-due.de

,

Christoph Hirschhäuser *

University Duisburg-Essen, Universitätsstraße 7, 45117 Essen, Germany Email: Christoph.Hirschhaeuser@uni-due.de

› Author Affiliations

Abstract

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Dedicated to Prof. Hans-Günther Schmalz on the occasion of his 60^th birthday.

Abstract

The ability to assemble organic molecules one carbon atom at a time has been a long-held dream for chemists. Modern boronate homologations with chiral carbenoids allow for the assembly-line synthesis of long chiral alkyl chains with excellent control over individual stereocenters. Nevertheless, heteroatom rich motives present a serious synthetic challenge to this approach. Interestingly, older methods based on substrate-controlled homologations of chiral boronic esters or umpolung of a carbonyl nucleophile can offer complementary solutions. A combination of these approaches might thus extend the range of possible targets currently within grasp of a C₁-based synthesis. Link to video abstract: https://www.youtube.com/watch?v=PH_HBrqQwtg .

1 Introduction

2 Substrate Control: Stereoselective Addition of d₁-Reagents to Aldehydes

3 Stereocontrol by Chiral Auxiliary/Director: The Matteson Boronate Homologation

4 Reagent Control: Moving Chiral Information to the Carbenoid

5 Conclusions and Outlook

Key words

homologation - assembly-line synthesis - chiral carbenoid - boronic ester - Matteson homologation - Dondoni homologation - Aggarwal homologation

Full Text

References

References

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Supplementary Material

Supporting Information

A Complementary Toolbox of Iterative Methods for the Stereo­selective Synthesis of Heteroatom-Rich Motives from C1-Building Blocks

A Complementary Toolbox of Iterative Methods for the Stereoselective Synthesis of Heteroatom-Rich Motives from C₁-Building Blocks