An Aluminum Hydride That Functions like a Transition-Metal Catalyst

Zhi Yang; Mingdong Zhong; Xiaoli Ma; Susmita De; Chakkittakandiyil Anusha; Pattiyil Parameswaran; Herbert W Roesky

doi:10.1002/anie.201503304

An Aluminum Hydride That Functions like a Transition-Metal Catalyst

Angew Chem Int Ed Engl. 2015 Aug 24;54(35):10225-9. doi: 10.1002/anie.201503304. Epub 2015 Jun 18.

Authors

Zhi Yang¹, Mingdong Zhong², Xiaoli Ma², Susmita De³, Chakkittakandiyil Anusha³, Pattiyil Parameswaran⁴, Herbert W Roesky⁵

Affiliations

¹ School of Chemical Engineering and Environment, Beijing Institute of Technology, 100081 Beijing (P.R. China). [email protected].
² School of Chemical Engineering and Environment, Beijing Institute of Technology, 100081 Beijing (P.R. China).
³ Department of Chemistry, National Institute of Technology Calicut, NIT Campus P.O., Calicut, Kerala, 673 601 (India).
⁴ Department of Chemistry, National Institute of Technology Calicut, NIT Campus P.O., Calicut, Kerala, 673 601 (India). [email protected].
⁵ Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, 37077 Göttingen (Germany). [email protected].

PMID: 26087711
DOI: 10.1002/anie.201503304

Abstract

The reaction of [LAlH2 ] (L=HC(CMeNAr)2 , Ar=2,6-iPr2 C6 H3 ) with MeOTf (Tf=SO2 CF3 ) resulted in the formation of [LAlH(OTf)] (1) in high yield. The triflate substituent in 1 increases the positive charge at the aluminum center, which implies that 1 has a strong Lewis acidic character. The excellent catalytic activity of 1 for the hydroboration of organic compounds with carbonyl groups was investigated. Furthermore, it was shown that 1 effectively initiates the addition reaction of trimethylsilyl cyanide (TMSCN) to both aldehydes and ketones. Quantum mechanical calculations were carried out to explore the reaction mechanism.

Keywords: aluminum; homogeneous catalysis; hydrides; hydroboration; hydrosilylation.