Mechanistic insight into Pd‐catalyzed asymmetric alkylation of indoles with diazoesters employing bipyridine‐N,N’‐dioxides as chiral controllers

Mechanistic insight into Pd‐catalyzed asymmetric alkylation of indoles with diazoesters employing bipyridine‐N,N’‐dioxides as chiral controllers Full article

Journal

Advanced Synthesis & Catalysis
ISSN: 1615-4169 , E-ISSN: 1615-4150

Output data

Year: 2024, Volume: 366, Number: 1, Pages: 121-133 Pages count : 13 DOI: 10.1002/adsc.202300845

Authors

Fukazawa Yasuaki ¹ , Vaganov Vladimir ² , Burykina Julia ³ , Fakhrutdinov Artem ³ , Safiullin Ruslan ² , Plasser Felix ¹ , Rubtsov Aleksandr ² , Ananikov Valentine ³ , Malkov Andrei V. ⁴

Affiliations

1	Loughborough University School of Science, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND
2	Perm State University, RUSSIAN FEDERATION
3	N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky prospect 47 Moscow 119991 Russia
4	Loughborough University, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND

Metal-catalyzed asymmetric alkylation of indoles with α-diazoesters is well-known, however, the underlying mechanisms of this reaction, particularly the origin of stereoselectivity, remain uncertain. For the Pd catalysis, we address this cutting-edge challenge from two complementary viewpoints – i) the molecular level regarding a single catalytically active Pd center; and ii) nano-level Pd species investigating the factors favoring the appearance of the preferred catalytic centers. The formation of the active catalytic species was monitored by structural methods (NMR and ESI-MS), and metal particles were characterized with electron microscopy (SEM, EDX). On the molecular level, chiral bipyridine-N,N’-dioxides proved to be competent chiral controllers. The kinetic and DFT computational data revealed a crucial role of water in the rate and selectivity determining steps and showed that the enantioselectivity of the process is controlled by the protodepalladation step. On the nano-scale, the important effect of catalyst precursor on the overall reaction performance was shown.

Fukazawa Y. , Vaganov V. , Burykina J. , Fakhrutdinov A. , Safiullin R. , Plasser F. , Rubtsov A. , Ananikov V. , Malkov A.V.
Mechanistic insight into Pd‐catalyzed asymmetric alkylation of indoles with diazoesters employing bipyridine‐N,N’‐dioxides as chiral controllers
Advanced Synthesis & Catalysis. 2024. V.366. N1. P.121-133. DOI: 10.1002/adsc.202300845 OpenAlex

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W4388865375

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