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A highly efficient synthesis of ( Z )‐1‐aryl‐2‐silyl‐1‐ stannylethenes and their conversion to ( E )‐2‐ arylethenyl‐, ( Z )‐2‐(2‐pyridyl)ethenyl‐ and allenyl‐silanes
Author(s) -
Endo Takanori,
Sasaki Fumio,
Hara Hisashi,
Suzuki Jyunko,
Tamura Shizuka,
Nagata Yoshikazu,
Iyoshi Tetsuro,
Saigusa Atsuhiro,
Nakano Taichi
Publication year - 2007
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1186
Subject(s) - silylation , chemistry , silane , aryl , silanes , trifluoroacetic acid , medicinal chemistry , trimethylsilyl , stannane , propargyl , methyllithium , iodide , alkyl , organic chemistry , catalysis
A Pd(dba) 2 –P(OEt) 3 combination allowed the silastannation of arylacetylenes, 1‐hexyne or propargyl alcohols with tributyl(trimethylsilyl)stannane to take place at room temperature, producing ( Z )‐2‐silyl‐1‐stannyl‐1‐substituted ethenes in high yields. Novel silyl(stannyl)ethenes were fully characterized by 1 H‐, 13 C‐, 29 Si‐ and 119 Sn‐NMR as well as infrared and mass analyses. Treatment of a series of ( Z )‐1‐aryl‐2‐silyl‐1‐stannylethenes and ( Z )‐1‐(3‐pyridyl)‐2‐silyl‐1‐stannylethene with hydrochloric acid or hydroiodic acid in the presence of tetraethylammonium chloride (TEACl) or tetrabutylammonium iodide (TBAI) led to the exclusive formation of ( E )‐trimethyl(2‐arylethenyl)silanes with high stereoselectivity. A similar reaction of ( Z )‐1‐(2‐anisyl)‐2‐silyl‐1‐stannylethene also produced E ‐type trimethyl[2‐(2‐anisyl)ethenyl]silane, while ( Z )‐trimethyl [2‐(2‐pyridyl)ethenyl]silane was produced exclusively from (Z)‐1‐(2‐pyridyl)‐2‐silyl‐1‐stannylethene. Protodestannylation of ( Z )‐1‐[hydroxy(phenyl)methyl]‐2‐silyl‐1‐stannylethene with trifluoroacetic acid took place via the β‐elimination of hydroxystannane, providing trimethyl(3‐phenylpropa‐1,2‐dienyl)silane quite easily. The destannylation products were also fully characterized. Copyright © 2007 John Wiley & Sons, Ltd.