C-Propargylation Overrides O-Propargylation in Reactions of Propargyl Chloride with Primary Alcohols: Rhodium-Catalyzed Transfer Hydrogenation

Tao Liang; Sang Kook Woo; Michael J Krische

doi:10.1002/anie.201603575

C-Propargylation Overrides O-Propargylation in Reactions of Propargyl Chloride with Primary Alcohols: Rhodium-Catalyzed Transfer Hydrogenation

Angew Chem Int Ed Engl. 2016 Aug 1;55(32):9207-11. doi: 10.1002/anie.201603575. Epub 2016 Jun 20.

Authors

Tao Liang¹, Sang Kook Woo¹, Michael J Krische²

Affiliations

¹ University of Texas at Austin, Department of Chemistry, 105 E 24th St. (A5300), Austin, TX, 78712-1167, USA.
² University of Texas at Austin, Department of Chemistry, 105 E 24th St. (A5300), Austin, TX, 78712-1167, USA. mkrische@mail.utexas.edu.

Abstract

The canonical SN 2 behavior displayed by alcohols and activated alkyl halides in basic media (O-alkylation) is superseded by a pathway leading to carbinol C-alkylation under the conditions of rhodium-catalyzed transfer hydrogenation. Racemic and asymmetric propargylations are described.

Keywords: alcohols; hydrogenation; reaction mechanisms; rhodium; synthetic methods.

Publication types

Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't

MeSH terms

Alcohols / chemistry*
Alkynes / chemistry*
Catalysis
Hydrogenation
Molecular Structure
Pargyline / analogs & derivatives
Pargyline / chemical synthesis*
Pargyline / chemistry
Propanols / chemistry*
Rhodium / chemistry*

Substances

Alcohols
Alkynes
Propanols
propargyl chloride
Pargyline
Rhodium

Grants and funding

R01 GM069445/GM/NIGMS NIH HHS/United States