Dimethoxymethylsilane, DMMS

Recent Literature

A copper hydride-catalyzed enantioselective reduction of α,β-unsaturated carboxylic acids provides various saturated β-chiral aldehydes in good yields, with high levels of enantioselectivity and broad functional group tolerance. A reaction pathway involving a ketene intermediate is proposed.
Y. Zhou, J. S. Bandar, R. Y. Liu, S. L. Buchwald, J. Am. Chem. Soc., 2018, 140, 606-609.

A direct enantioselective copper hydride (CuH)-catalyzed synthesis of β-chiral amides from α,β-unsaturated carboxylic acids and secondary amines under mild reaction conditions tolerates a variety of functional groups in the β-position including several heteroarenes. A subsequent iridium-catalyzed reduction to γ-chiral amines can be performed in the same flask.
A. Link, Y. Zhou, S. L. Buchwald, Org. Lett., 2020, 22, 5666-5670.

A direct asymmetric copper hydride (CuH)-catalyzed coupling of α,β-unsaturated carboxylic acids with aryl alkenes provides chiral α-aryl dialkyl ketones. The reaction tolerates various substrate substitution patterns, sensitive functional groups, and heterocycles.
Y. Zhou, J. S. Bandar, S. L. Buchwald, J. Am. Chem. Soc., 2017, 139, 8126-8129.

The combination of allene gas with inexpensive and environmentally benign hydrosilanes enables enantioselective ketone allylation reactions without stoichiometric quantities of an allylmetal reagent. This process is catalyzed by copper salts and commercially available ligands, operates without specialized equipment or pressurization, and tolerates a broad range of functional groups.
R. Y. Liu, Y. Zhou, Y. Yang, S. L. Buchwald, J. Am. Chem. Soc., 2019, 141, 2251-2256.

(R,R)-Ph-BPE ligated Cu catalyzes a chemo-, regio-, and enantioselective allylation of ketones with 1,3-dienes in the presence a hydrosilane to provide chiral homoallylic tertiary alcohols under very mild conditions with good functional group tolerance. 1,3-dienes as the latent allylic nucleophiles avoid the the use of stoichiometric quantities of allylmetal reagents.
B. Fu, X. Yuan, Y. Li, Y. Wang, Q. Zhang, T. Xiong, Q. Zhang, Org. Lett., 2019, 21, 3576-3580.

A highly selective copper-catalyzed reductive hydroxymethylation of 1,3-dienes with CO₂ provides chiral all-carbon acyclic quaternary stereocenters. A variety of readily available 1,1-disubstituted 1,3-dienes, as well as a 1,3,5-triene, undergo the reaction with high chemo-, regio-, E/Z-, and enantioselectivities and good functional group tolerance.
X.-W. Chen, L. Zhu, Y.-Y. Gui, K. Jing, Y.-X. Jiang, Z.-Y. Bo, Y. Lan, J. Li, D.-G. Yu, J. Am. Chem. Soc., 2019, 141, 18825-18835.

Zirconocene hydride catalyzes a mild method for the semireduction of both secondary and tertiary amides to imines. While secondary amides furnish a diverse array of imines in very good yield with excellent chemoselectivity, a reductive transamination of tertiary amides is also achievable in the presence of a primary amine at room temperature.
R. A. Kehner, G. Zhang, L. Bayeh-Romero, J. Am. Chem. Soc., 2023, 145, 4921-4927.

A copper-hydride-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. The reaction avoids a typically challenging 1,2-siloxane elimination step, proceeds at ambient temperature, and tolerates a variety of metal-, acid-, or base-sensitive functional groups.
R. Y. Liu, M. Bae, S. L. Buchwald, J. Am. Chem. Soc., 2018, 140, 1627-1631.

In a direct route for the synthesis of alkyl-substituted chiral aziridines from achiral starting materials, readily accessed allylic hydroxylamine esters undergo copper hydride-catalyzed intramolecular hydroamination with a high degree of regio- and enantiocontrol to afford the aziridine products in good to excellent yields in highly enantioenriched form.
H. Wang, J. C. Yang, S. L. Buchwald, J. Am. Chem. Soc., 2017, 139, 8428-8431.

The use of 1,2-benzisoxazole as a practical electrophilic primary amine source enables a mild and general copper-hydride-catalyzed hydroamination of alkenes and alkynes to form primary amines. This method provides access to a broad range of chiral α-branched primary amines and linear primary amines.
S. Guo, J. C. Yang, S. L. Buchwald, J. Am. Chem. Soc., 2018, 140, 15976-15984.

A highly enantio- and regioselective Ni-catalyzed hydroamination of readily available unactivated alkenes bearing weakly coordinating native amides or esters provides β- or γ-amino acid derivatives and 1,2- or 1,3-diamines for both terminal and internal unactivated alkenes and a broad amine coupling partner scope. The mild reaction is well suited for late-stage functionalization.
C. Lee, H.-J. Kang, H. Seo, S. Hong, J. Am. Chem. Soc., 2022, 144, 9091-9100.

A NiH-catalyzed strategy for the hydroamidation of alkynes with dioxazolones allows convenient access to synthetically useful secondary enamides in (E)-anti-Markovnikov or Markovnikov selectivity. The reaction is viable for both terminal and internal alkynes and also tolerates a range of functional groups. The presence of H₂O is crucial for high catalyst turnovers.
X. Lyu, J. Zhang, D. Kim, S. Seo, S. Chang, J. Am. Chem. Soc., 2021, 143, 5867-5877.

A copper hydride-catalyzed, enantioselective, intramolecular hydroalkylation of halide-tethered styrenes enables the synthesis of enantioenriched cyclobutanes, cyclopentanes, indanes, and six-membered N- and O-heterocycles.
Y.-M. Wang, N. C. Bruno, A. L. Placeres, S. Zhu, S. L. Buchwald, J. Am. Chem. Soc., 2015, 137, 10524-10527.

Highly efficient catalyst-tuned regio- and enantioselective hydroalkylation reactions of readily available 3-pyrrolines provide chiral C2-alkylated pyrrolidines in the presence of a Co catalyst and C3-alkylated pyrrolidines in the presence of a Ni catalyst. These divergent methods use readily available catalysts, chiral BOX ligands, and reagents.
X. Wang, J. Xue, Z.-Q. Rong, J. Am. Chem. Soc., 2023, 145, 15456-15464.

An efficient copper hydride (CuH)-catalyzed enyne-nitrile coupling reaction provides polysubstituted N-H pyrroles bearing a broad range of functional groups in good yields with high regioselectivity. The Cu-based catalyst promotes both the initial reductive coupling and subsequent cyclization steps.
Y. Zhou, L. Zhou, L. T. Jesikiewicz, P. Liu, S. L. Buchwald, J. Am. Chem. Soc., 2020, 142, 9908-9914.