%0 Journal Article
%A Kownacki, Ireneusz
%A Orwat, Bartosz
%A Marciniec, Bogdan
%D 2014
%T Iridium-Promoted Conversion of Chlorosilanes to Alkynyl
Derivatives in a One-Pot Reaction Sequence
%U https://acs.figshare.com/articles/journal_contribution/Iridium_Promoted_Conversion_of_Chlorosilanes_to_Alkynyl_Derivatives_in_a_One_Pot_Reaction_Sequence/2280741
%R 10.1021/om500320t.s001
%2 https://acs.figshare.com/ndownloader/files/3917142
%K iodosilane molecules
%K silylative
%K SiR 1nCl
%K NMR studies
%K terminal alkyne
%K equimolar reaction
%K Alkynyl Derivatives
%K iridium center
%K conversion
%K oxidative addition
%K chlorosilane
%X By making use of the catalytic potential
of the iridium system
[{Ir(μ-Cl)(CO)2}2]/NEt(i-Pr)2 in the synthesis of silyl-functionalized alkynes
via silylative coupling of terminal alkynes/diynes with iodosilanes,
we propose a new protocol allowing employment of various mono- and
dichlorosilanes as reagents. The process is based on a sequence of
two reactions occurring simultaneously: i.e., conversion of initial
chlorosilane (SiR1nCl4–n) to the appropriate iodosilane via Cl/I nucleophilic
substitution and its further conversion to a silylalkyne derivative
((SiR1n(CCR2)4–n) via iridium-catalyzed silylative
coupling with terminal alkyne. Under optimum conditions, the method
has proved to be effective and versatile in the conversion of a wide
range of chlorosilanes to a rich portfolio of various corresponding
alkynyl-functionalized silicon derivatives. Additionally, NMR studies
of the equimolar reaction of a well-defined iridium(I) alkynyl precursor
with Me3Si–I revealed that Si–I bond
activation in iodosilane molecules occurred via oxidative addition
to the iridium center.
%I ACS Publications