A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes
Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.
Naganawa, Yuki,Nakajima, Yumiko,Sakamoto, Kei
supporting information
p. 601 - 606
(2021/01/13)
Steroidal Silicon Side-Chain Analogues as Potential Antifertility Agents
A number of silicon-substituted analogues of ethynylestradiol that exhibit modified and enhanced biological activities have been synthesized.Particularly noteworthy are a group of estradiol analogues that exhibit high antifertility potency and markedly reduced estrogenic activity.The best compounds synthesized are 17α-estradiol (5) and 17α-estradiol (33), which show a separation of antifertility from estrogenic activity in the rat.The results of structure-activity studies indicate a good correlation between the observed biological activities and the calculated van der Waals volumes of the three variable silicon substituents.
Peters, Richard H.,Crowe, David F.,Tanabe, Masato,Avery, Mitchell A.,Chong, Wesley K. M.
p. 646 - 652
(2007/10/02)
THE REACTIONS OF HYDROSILANES WITH TRIFLUOROPROPENE AND PENTAFLUOROSTYRENE CATALYZED BY RUTHENIUM, RHODIUM AND PALLADIUM COMPLEXES
The reactions of hydrosilanes with trifluoropropene (TFP) and pentafluorostyrene (PFS) catalyzed by Ru3(CO)12 or RhCl(PPh3)3 give β-Rf-vinylsilane (1) and/or β-Rf-ethylsilane (2) (Rf=perfluorocarbon group).The 1/2 ratio is highly dependent on the nature of hydrosilane used.The ruthenium catalyst favors the formation of 1 compared with the rhodium catalyst.Neither α-Rf-vinylsilane nor α-Rf-ethylsilane was formed at all.Possible mechanisms which can accommodate characteristic features of these reactions are discussed.The hydrosilylation of TFP with dichloromethylsilane catalyzed by PdCl2(PhCN)2/2PPh3 gives the α-adduct (9a) exclusively, and this is transformed to the corresponding dialkoxysilanes, silane diol, oligosilane diols and cyclic oligosiloxanes.
Ojima, Iwao,Fuchikami, Takamasa,Yatabe, Momoko
p. 335 - 346
(2007/10/02)
CATALYTIC REARRANGEMENT REACTIONS BETWEEN CHLORO- AND ALKOXY-SILANES
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Nilolaev, G. A.,Mileshkevich, V. P.,Vainshtein, P. M.,Shmeleva, O. A.
p. 1867 - 1870
(2007/10/02)
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