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Chemicals >> Reducing Agents > Silanes

Diethoxymethylsilane, DEMS

see also: dimethoxymethylsilane

Recent Literature

Chiral rhodium-bis(oxazolinyl)phenyl complexes catalyze the conjugate hydrosilylation of 3,3-diarylacrylate derivatives to prepare optically active 3,3-diarylpropanoate derivatives in high yields and high enantioselectivities.
K. Itoh, A. Tsuruta, J.-i. Ito, Y. Yamamoto, H. Nishiyama, J. Org. Chem., 2012, 77, 10914-10919.

Selective conjugate reductions of α,β-unsaturated aldehydes were achieved in the presence of rhodium(bisoxazolinylphenyl) complexes as catalysts and alkoxyhydrosilanes as reducing agents.
Y. Kanazawa, H. Nishiyama, Synlett, 2006, 3343-3345.

A nickel-catalyzed, multicomponent regio- and enantioselective hydroformylation and carbonylation using chloroformate as a safe CO source provides a wide variety of unsymmetrical dialkyl ketones bearing a functionalized α-stereocenter, including enantioenriched chiral α-aryl ketones and α-amino ketones.
J. Chen, S. Zhu, J. Am. Chem. Soc., 2021, 143, 14089-14096.

Treatment of β,β-disubstituted-α,β-unsaturated ketones bearing a ketone residue with in situ generated, catalytic CuH ligated by a nonracemic ligand leads to cyclic aldol products with three newly created adjacent chiral centers. Excellent diastereoselectivities and enantioselectivities are obtained for several examples studied.
B. H. Lipshutz, B. Amorelli, J. B. Unger, J. Am. Chem. Soc., 2008, 130, 14378-14379.

A CuH-catalyzed hydroamination of alkenes using an amine transfer reagent and a silane provides chiral amines with high efficiency and stereoselectivity. However, the current technology has been limited to dialkylamine transfer reagents (R2NOBz). A modified type of monoalkylamine transfer enabled the synthesis of chiral secondary amines, including those derived from amino acid esters, carbohydrates, and steroids.
D. Niu, S. L. Buchwald, J. Am. Chem. Soc., 2015, 137, 9716-9721.

A highly enantio- and regioselective copper-catalyzed hydroamination reaction of alkenes with hydroxylamine esters in the presence of diethoxymethylsilane enables the conversion of a wide variety of substituted styrenes, including trans-, cis-, and β,β-disubstituted styrenes, to yield α-branched amines. In addition, aliphatic alkenes gave exclusively the anti-Markovnikov hydroamination products.
S. Zhu, N. Niljianskul, S. L. Buchwald, J. Am. Chem. Soc., 2013, 135, 15746-15749.

S. Zhu, N. Niljianskul, S. L. Buchwald, J. Am. Chem. Soc., 2013, 135, 15746-15749.

Unprecedented chemoselective reductions of phosphine oxides to phosphines with inexpensive silanes proceed smoothly in the presence of catalytic amounts of specific phosphoric acid esters. The reaction tolerates ketones, aldehydes, olefins, nitriles, and esters under the optimized conditions.
Y. Li, L.-Q. Lu, S. Das, S. Pisiewicz, K. Junge, M. Beller, J. Am. Chem. Soc., 2012, 134, 18325-18329.

A diastereo- and enantioselective CuH-catalyzed method for the preparation of highly functionalized indolines offers mild reaction conditions and high degree of functional group compatibility. This method is highly valuable for the synthesis various cis-2,3-disubstituted indolines in high yield and enantioselectivity.
E. Ascic, S. L. Buchwald, J. Am. Chem. Soc., 2015, 137, 4666-4669.