Categories: C-Si Bond Formation > Siloxanes
Synthesis of vinylsiloxanes
Related |
Recent Literature
Grubbs' first-generation Ru metathesis complex
catalyses the hydrosilylation of terminal alkynes. The reaction exhibits an
interesting selectivity profile that is dependent on the reaction concentration
and more importantly on the silane employed.
C. S. Arico, L. R. Cox, Org. Biomol. Chem., 2004, 2,
2558-2562.
Low catalyst loadings of (IPr)Pt(allyl ether) display enhanced activity and
regioselectivity for the hydrosilylation of terminal and internal alkynes.
Reactions lead to exquisite regioselectivity in favor of the cis-addition
product on the less hindered terminus of terminal and internal alkynes.
G. Berthon-Gelloz, J.-M. Schumers, G. De Bo, I. E. Markó, J. Org. Chem., 2008,
73, 4190-4197.
A silyl-Heck reaction allows the preparation of vinyl silyl ethers and
disiloxanes rom aryl-substituted alkenes and related substrates using a
commercially available catalyst system and mild conditions. This work represents
a highly practical means of accessing diverse classes of vinyl silyl ether
substrates in an efficient and direct manner with complete regiomeric and
geometric selectivity.
S. E. S. Martin, D. A. Watson, J. Am. Chem. Soc., 2013,
135, 13330-13333.
Ruthenium alkylidenes catalyze regio- and stereoselective dehydrogenative
silylations and hydrosilylations of vinylarenes with alkoxysilanes. Depending on
the ligand, the method offers selective access to either (E)-vinylsilanes
or β-alkylsilanes with high regio- and stereocontrol.
A. Bokka, J. Jeon, Org. Lett.,
2016, 18, 5324-5327.
A bench-stable alkyl bisphosphine Mn(I) complex catalyzes an additive-free
Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes. A broad variety
of aromatic and aliphatic alkenes was efficiently and selectively converted into
E-vinylsilanes and allylsilanes, respectively, at room temperature.
S. Weber, M. Glavic, B. Stöger, E. Pittenauer, M. Podewitz, L. F. Veiros, K.
Kirchner, J. Am. Chem. Soc.,
2021, 143, 17825-17832.
A well-defined low-valent cobalt(I) catalyst [HCo(PMe3)4]
enables a highly regio- and stereoselective hydrosilylation of internal alkynes.
The reaction provides in many cases a single hydrosilylation isomer for various
hydrosilanes and unsymmetrical alkynes.
A. Rivera-Hernández, B. J. Fallon, S. Ventre, C. Simon, M.-H. Tremblay, G.
Gontard, E. Derat, M. Amatore, C. Aubert, M. Petit, Org. Lett.,
2016, 18, 4242-4245.
Palladium catalyzes a highly regio- and stereoselective hydrosilylation
applicable to a broad range of electron-deficient alkynes. The resulting
α-silylalkenes can be further transformated using particularly Hiyama coupling
and stereoinverting iododesilylation followed by Suzuki-Miyaura coupling, which
enables stereodivergent syntheses of α-arylenoates.
Y. Sumida, T. Kato, S. Yoshida, T. Hosoya, Org. Lett., 2012,
14, 1552-1555.
In the presence of Pd(0) and a phosphine, a hydrosilylation of 1,3-enynes
with Me2SiHCl yields dienylsilanes with (E)-configuration and
with the silicon group added to the internal alkyne carbon atom. Subsequent
hydrolysis gives silanols, that serve as precursors to conjugated dienes with
different substitution patterns.
H. Zhou, C. Moberg, Org. Lett., 2013,
15, 1444-1447.