Catalytic carbonyl hydrosilylations via a titanocene borohydride-PMHS reagent system

Catalytic carbonyl hydrosilylations via a titanocene borohydride-PMHS reagent system

Catal. Sci. Technol., 2017, Advance Article

DOI: 10.1039/C7CY01088E, Paper

Godfred D. Fianu, Kyle C. Schipper, Robert A. Flowers II
Catalytic amounts of titanocene(III) borohydride, generated under mild conditions from commercially available titanocene dichloride, in concert with a stoichiometric hydride source is shown to effectively reduce aldehydes and ketones to their respective alcohols in aprotic media.

From the journal:

• Catalysis Science & Technology

Catalytic carbonyl hydrosilylations viaa titanocene borohydride–PMHS reagent system

Godfred D. Fianu,a  Kyle C. Schippera  and  Robert A. Flowers II*a 

 Author affiliations

*Corresponding authors

aDepartment of Chemistry, Lehigh University, Bethlehem, USA
E-mail: rof2@lehigh.edu

Abstract

Reduction of a wide range of aldehydes and ketones with catalytic amounts of titanocene borohydride in concert with a stoichiometric poly(methylhydrosiloxane) (PMHS) reductant is reported. Preliminary mechanistic studies demonstrate that the reaction is mediated by a reactive titanocene(III) complex, whose oxidation state remains constant throughout the reaction.

Godfred Fianu

Lehigh University , Bethlehem · Department of Chemistry

Robert A Flowers

Danser Distinguished Faculty Chair in Chemistry and Deputy Provost for Faculty Affairs

Lehigh University , Bethlehem · Department of Chemistry

Lehigh University

Department of Chemistry

Bethlehem, United States

Phenyl methanol (2-c)
Phenyl methanol (2-c) was prepared from benzaldehyde (1-c) by the procedure outlined
in GP1. NMR analysis showed 100% conversion in 1 hour. 86% isolated yield of alcohol
product was obtained after complete workup.

1H NMR (400 MHz, CDCl3) δ 7.37 – 7.26 (m,5H), 4.59 (s, 2H), 2.99 (s, 1H).

13C NMR (101 MHz, CDCl3) δ 140.92, 128.56, 127.60, 127.07,77.52, 77.20, 76.88, 65.04.

 

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