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Gold‐Catalyzed Intermolecular Anti‐Markovnikov Hydroamination of Alkylidenecyclopropanes
Author(s) -
Timmerman Jacob C.,
Robertson Bradley D.,
Widenhoefer Ross A.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201410871
Subject(s) - hydroamination , markovnikov's rule , regioselectivity , chemistry , alkene , nucleophile , phosphine , catalysis , medicinal chemistry , organic chemistry , intermolecular force , molecule
The cationic gold phosphine complex [{PCy 2 ( o ‐biphenyl)}Au(NCMe)] + SbF 6 − (Cy=cyclohexyl) catalyzes the intermolecular, anti‐Markovnikov hydroamination reaction of monosubstituted and cis ‐ and trans ‐disubstituted alkylidenecyclopropanes (ACPs) with imidazolidin‐2‐ones and other nucleophiles. This reaction forms 1‐cyclopropyl alkylamine derivatives in high yield and with high regio‐ and diastereoselectivity. NMR spectroscopic analysis of gold π‐ACP complexes and control experiments point to the sp hybridization of the ACP internal alkene carbon atom as controlling the regiochemistry of the ACP hydroamination reaction.