Carbostannolysis mediated by bis(pentamethylcyclopentadienyl)lanthanide catalysts. Utility in accessing organotin synthons

Stephen D. Wobser, Casey J. Stephenson, Massimiliano Delferro, Tobin J. Marks

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Facile carbon-tin bond activation in the reaction of 2-(trimethylstannyl) pyridine (1) with the organolanthanide complexes Cp*2LaCH(TMS) 2 (2a) and [Cp*2LaH]2 (2b) yields Cp*2La(2-pyridyl) (3), as well as Me3SnCH(TMS) 2 and Me3SnH, respectively. At room temperature, ethylene then undergoes insertion into the resulting La-C(pyridyl) bond followed by carbostannolysis to catalytically generate 2-(2-(Me3Sn)ethyl)pyridine (4) or, with extended reaction times, 6-ethyl-2-(2-(trimethylstannyl)ethyl) pyridine (5). In contrast to 1, 6-methyl-2-(trimethylstannyl)pyridine (6) is unreactive, likely reflecting steric constraints. With terminal alkynes, this catalytic heterocycle-SnMe3 activation/carbostannylation process affords tin-functionalized conjugated enynes. Thus, at 60 C 2b catalyzes the conversion 1 + 1-hexyne to yield (E)-2-butyl-1-(Me3Sn)-oct-1-en-3-yne in a 60:1 ratio E:Z isomer ratio. This reaction is available to α-monosubstituted and α-disubstituted terminal alkynes, while α-trisubstituted alkynes are too hindered for reaction. The catalytic cycle is proposed to proceed via a spectroscopically detectable Me 3Sn-alkynyl intermediate which undergoes insertion into a Cp*2La-alkynyl bond to produce the conjugated alkynyl product, which is subsequently protonolyzed from the Cp*2La center by a new terminal alkyne substrate molecule. NMR spectroscopic and kinetic data support the proposed pathway and indicate turnover-limiting alkyne insertion.

Original languageEnglish
Pages (from-to)1317-1327
Number of pages11
JournalOrganometallics
Volume32
Issue number5
DOIs
Publication statusPublished - Mar 11 2013

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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