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.
The combination of amide activation by Tf2O with B(C6F5)3-catalyzed
hydrosilylation with TMDS enables a one-pot reduction of secondary amides to
amines under mild conditions with broad applicability and excellent
chemoselectivity for many sensitive functional groups.
P.-Q. Huang, Q.-W. Lang, Y.-R. Wang, J. Org. Chem.,
2016,
81, 4235-4243.
Tris(pentafluorophenyl)boron B(C6F5)3 is an
effective catalyst for the reduction of tertiary and N-phenyl secondary
amides in the presence of a silane. Various amides can be reduced in near
quantitative yield, with minimal purification, at low temperatures, and with
short reaction times. This reduction tolerates alkenes, nitro groups, and aryl
halides, including aryl iodides.
R. C. Chadwick, V. Kardelis, P. Lim, A. Adronov, J. Org. Chem., 2014,
79, 7728-7733.
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.
A readily accessible thiourea organocatalyst catalyzes reductive condensations
of alcohols with aldehydes/ketones to provide ethers without homocoupling of the
carbonyl component in the presence of HCl and 1,1,3,3-tetramethyldisiloxane as a
convenient reducing reagent. This strategy is applicable to challenging
substrate combinations and exhibits functional group tolerance.
C. Zhao, C. A. Sojdak, W. Myint, D. Seidel, J. Am. Chem. Soc., 2017,
139, 10224-10227.
The conversion of nitriles to silylated primary amines was achieved in the
presence of TMDS as the reducing agent, a catalytic
amount of Co(OPiv)2, and an isocyanide ligand. Acid hydrolysis or treatment with
acid chlorides provided the corresponding primary amines or imides in good yields.
A. Sanagawa, H. Nagashima, Org. Lett.,
2019, 21, 287-291.
Air-stable cationic hemiboronic acids catalyze chemoselective reduction of
enones. Depending on the silane reducing agent, either the conjugate reduction
products or the fully reduced products can be obtained in high selectivity.
J. P. G. Rygus, D. B. Boateng, D. G. Hall, Synlett, 2023,
34,
2215-2219.
Nanoparticles formed from PdCl2 in the presence of
tetramethyldisiloxane (TMDS) on water enable a mild and environmentally
attractive dehalogenation of functionalized aryl halides. The reaction medium
with the catalyst can be recycled.
A. Bhattacharjya, P. Klumphu, B. H. Lipshutz, Org. Lett.,
2015,
17, 1122-1125.
The counteranions of CuCl2 functioned as a chloride source in a
reductive chlorination of carboxylic acids in the presence of a gallium(III)
catalyst and a hydrosiloxane.
N. Sakai, T. Nakajima, S. Yoneda, T. Konakahara, Y. Ogiwara, J. Org. Chem.,
2014,
79, 10619-10623.
The combination of 1,1,3,3-tetramethyldisiloxane (TMDS) and trimethylbromosilane
(Me3SiBr) enabled a direct bromination of carboxylic acids in the
presence of indium bromide (InBr3) as catalyst. The reducing system
was tolerant to several functional groups and produced the corresponding alkyl
bromides in very good yields.
T. Moriya, S. Yoneda, K. Kawana, R. Ikeda, T. Konakahara, N. Sakai, Org. Lett., 2012,
14, 4842-4845.
A highly effective indium(III)-catalyzed reductive bromination or iodination of
various carboxylic acids with 1,1,3,3-tetramethyldisiloxane (TMDS) and a halogen
source tolerates many functional groups. This indium catalytic system is also
applicable to the reductive iodination of aldehyded, acyl chlorides, and esters.
Furthermore, this reducing system can be applied to the one-pot synthesis of
alkyl halides and amine derivatives.
T. Moriya, S. Yoneda, K. Kawana, R. Ikeda, T. Konakahara, N. Sakai, J. Org. Chem., 2013,
78, 10642-10650.
Indium(III)-catalyzed reductive iodination or bromination of carboxylic acids
enables a one-pot preparation of alkyl cyanides from carboxylic acids via alkyl
iodides or alkyl bromides.
T. Moriya, K. Shoji, S. Yoneda, R. Ikeda, T. Konakahara, N. Sakai, Synthesis, 2013, 45,
3233-3238.
A reducing system combined with InBr3 and
1,1,3,3-tetramethyldisiloxane (TMDS) enables a direct thioetherification of
various aromatic carboxylic acids and thiols in a one-pot procedure, whereas a
system combined with InI3 and TMDS underwent thioetherification of
aliphatic carboxylic acids with thiols.
N. Sakai, T. Miyazaki, T. Sakamoto, T. Yatsuda, T. Moriya, R. Ikeda, T.
Konakahara, Org. Lett., 2012,
14, 4366-4369.
Iridium-catalyzed hydrosilylation of tertiary amides followed by
acid-mediated condensation with active methylene compounds provides
multifunctionalized non-N-containing products. This scalable method is
broad in scope and shows remarkable chemoselectivity for the amide group in the
presence of functionalities such as ester, cyano, nitro, silyl dienol ether, and
ketone.
D.-P. Wu, W. Ou, P.-Q. Huang, Org. Lett.,
2022, 24, 5366-5371.
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.
Y. Li, S. Das, S. Zhou, K. Junge, M. Beller, J. Am. Chem. Soc., 2012,
134, 9727-9732.
Phosphine oxides are selectively reduced to phoshphines in the presence of other
reducible functional groups such as ketones, esters, and olefins using
tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper
complexes. Based on this transformation, an efficient one pot reduction/phosphination
domino sequence generates functionalized aromatic and aliphatic phosphines in
good yields.
Y. Li, S. Das, S. Zhou, K. Junge, M. Beller, J. Am. Chem. Soc., 2012,
134, 9727-9732.
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.
