Synlett 2019; 30(11): 1275-1288
DOI: 10.1055/s-0037-1612257
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© Georg Thieme Verlag Stuttgart · New York

Cascades Involving anti-Carbopalladation Steps: From Our Initial Hypothesis to Natural Product Synthesis

Theresa Schitter
,
Andreas Reding
,
Daniel B. Werz*
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany   Email: d.werz@tu-braunschweig.de
› Author Affiliations
This research was supported by the Deutsche Forschungsgemeinschaft (DFG grant WE 2932/7-1 to D.B.W.).
Further Information

Publication History

Received: 10 January 2019

Accepted: 30 January 2019

Publication Date:
19 March 2019 (online)

These authors contributed equally to this work.

Abstract

Our endeavors in the design, realization and application of a formal anti-carbopalladation of alkynes are summarized. Whereas numerous examples of syn-carbopalladation steps embedded in cascade reactions are known, there have been almost no examples of the corresponding anti-carbopalladation steps. From a personal perspective, this account provides insights on the original considerations and hypotheses, and their validation or invalidation by experimental and computational means. This account also aims at clarifying how different ideas have been developed and how novel reaction sequences paving the way to a plethora of different scaffolds have been designed. The reader will recognize the importance of the interplay between elucidating reaction mechanisms and developing novel methodologies. As a result, useful methods to create homo- and heterotetrasubstituted double bonds have been developed. The broad versatility of these methods has been demonstrated by a novel total synthesis of the indole alkaloid (+)-lysergol.

1 Introduction

2 Initial Studies

3 Various Termination Steps

4 Termination with Heteronucleophiles

5 Natural Product Synthesis

6 anti-Carbopalladations Realized by the Lautens Lab

7 Conclusion and Outlook

 
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