Silicon Hydride Reductions

Hydrogen Donor Abilities of the Group 14 Hydrides,
   Chatgilialoglu, C.; Newcomb, M. Adv. Organometal. Chem. 1999, 44, 67-112. a)
Organosilanes as Radical-Based Reducing Reagents in Synthesis,
   C. Chatgilialoglu Acc. Chem. Res. 1992, 25, 188.
Applications of Ionic Hydrogenations to Organic Synthesis,
   D. N. Kursanov, Z. N. Parnes and N. M. Loim, Synthesis 1974, 663.
Hydrosilanes as Reducing Agents,
   Y. Nagai, Org. Prep. Proc. Int. 1980, 12, 13.
Controlling Benzylic and Anomeric Functionality and Stereochemistry: Methodology and Syntheses Utilizing Intramolecular Ionic Hydrogenation,
   McCombie, S. W.; Ortiz, C.; Cox, B.; Ganguly, A. K. Synlett 1993, 541.
Chemo- and Enantioselective Hydrosilylation of Carbonyl and Imino Groups. An Emphasis on Non-Traditional Catalyst Systems,
   Carpentier, J.-F.; Bette, V. Curr. Org. Chem. 2002, 6, 913-36.
Recent Advances in the Asymmetric Hydrosilylation of Ketones, Imines, and Electrophilic Double Bonds
  Riant, O.; Mostefai, N.; Courmarcel, J. Synthesis 2004, 2943-58.

  Silyl hydrides are very weak hydride donors (they are stable even to mild acids and oxidizing agents) and will not react with any neutral carbonyl compounds or imines. It is, however, possible to catalyze the reactions, either using Lewis or protic acids, or nucleophilic catalysts. Thus silyl hydrides will donate hydride to protonated carbonyl groups and most types of stabilized carbonium ions. Amine complexes of boranes (Me3N·BH3) can also perform similar reductions.

Ionic Hydride Reductions


Reduction of Hemiacetals - Synthesis of Camptothecin: Curran, D. P.; Ko, S. B.; Josien, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2683.


Reduction of hemiaminals - Anatoxin A: Brenneman, G. B.; Martin, S. F. Org. Lett. 2004, 6, 1329. DOI


Radical Chain Reductions with Silyl Hydrides.

Tris(trimethylsilyl)silane: Chatgilialoglu, JOC., 1988, 53, 3641; TL, 1989, 30, 2733. Giese, OS, 1991, 70, 164.


Bilobalide: Deoxygenation of Epoxides: Corey, JACS, 1987, 109, 7534.