Tetramethyldisiloxane (TMDSO, TMDS)
Recent Literature
1,1,3,3-tetramethyldisiloxane and 1,2-bis(dimethylsilyl)benzene are found to be
effective reducing agents for a platinum-catalyzed reduction of carboxamides to
amines. The reaction tolerates other reducible functional groups such as NO2,
CO2R, CN, C═C, Cl, and Br. The product is obtained by simple
extraction.
S. Hanada, E. Tsutsumi, Y. Motoyama, H. Nagashima, J. Am. Chem. Soc., 2009,
131, 15032-15040.
A triruthenium cluster catalyzes the reaction of secondary amides with
hydrosilanes, yielding a mixture of secondary amines, tertiary amines, and silyl
enamines. Production of secondary amines with complete selectivity is achieved
by the use of higher concentration of the catalyst and bifunctional hydrosilanes
such as 1,1,3,3-tetramethyldisiloxane followed by acidic workup.
S. Hanada, T. Ishida, Y. Motoyama, H. Nagashima, J. Org. Chem.,
2007,
72, 7551-7559.
TMDS is an efficient hydride source for the reduction of tertiary and secondary
phosphine oxides using a catalytic amount of Ti(OiPr)4. All
classes of tertiary phosphine oxides, such as triaryl, trialkyl, and diphosphine
were effectively reduced.
M. Berthod, A. Favre-Réguillon, J. Mohamad, G. Mignani, G. Docherty, M. Lemaire, Synlett, 2007,
1545-1548.
A cobalt-catalyzed hydroazidation of α,α-disubstituted olefins with commercially
available azide sources provides tertiary azides in useful yields and tolerates
a variety of functional groups.
B. Gaspar, J. Waser, E. M. Carreira, Synthesis, 2007,
3839-3845.
A highly Marknovikov selectiv conversion of various olefins to azides
was achieved using a cobalt catalyst, 3 equiv of TsN3 as
nitrogen source and simple silanes (PhSiH3, TMDSO).
J. Waser, H. Nambu, E. M. Carreira, J. Am. Chem. Soc., 2005,
127, 8294-8295.
