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A Ligand‐Free Pt 3 Cluster Catalyzes the Markovnikov Hydrosilylation of Alkynes with up to 10 6 Turnover Frequencies
Author(s) -
RiveroCrespo Miguel A.,
LeyvaPérez Antonio,
Corma Avelino
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605520
Subject(s) - markovnikov's rule , hydrosilylation , chemistry , catalysis , combinatorial chemistry , ligand (biochemistry) , organic chemistry , medicinal chemistry , regioselectivity , biochemistry , receptor
Abstract The Pt‐catalyzed hydrosilylation of alkynes is the procedure of choice to obtain vinylsilanes, and is claimed to be the most relevant application of Pt in organic synthesis. More than half a century after its discovery, only β‐vinylsilanes ( anti ‐Markovnikov addition) are obtained with simple Pt catalysts, whereas α‐vinylsilanes (Markovnikov addition) remain elusive compounds. Here the catalysis of the Markovnikov hydrosilylation of terminal alkynes by Pt 3 clusters, in parts‐per‐million amounts, to give a wide variety of α‐vinylsilanes in reasonable isolated yields and with turnover frequencies that can reach up to one million per hour is reported. Moreover, these α‐vinylsilanes are reactive in well‐stablished C−C bond‐forming cascade reactions, in which the corresponding β‐isomers are unreactive. Besides its efficiency and synthetic usefulness, this catalytic system is an excellent example of how the atom‐by‐atom aggregation of a catalytic metal leads to a different selectivity for a given reaction