‡ 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
Key words
palladium -
anti-carbopalladation - cascade - domino reaction - mechanistic studies - reaction design
- heterocycles - lysergol
