Enantioselective regiospecific addition of propargyltrichlorosilane to aldehydes catalyzed by biisoquinoline N, N'-dioxide

Noble Brako; Sreerag Moorkkannur Narayanan; Amber Burns; Layla Auter; Valentino Cesiliano; Rajeev Prabhakar; Norito Takenaka

doi:10.3762/bjoc.20.255

Enantioselective regiospecific addition of propargyltrichlorosilane to aldehydes catalyzed by biisoquinoline N, N'-dioxide

Beilstein J Org Chem. 2024 Nov 25:20:3069-3076. doi: 10.3762/bjoc.20.255. eCollection 2024.

Authors

Noble Brako¹, Sreerag Moorkkannur Narayanan², Amber Burns¹, Layla Auter¹, Valentino Cesiliano², Rajeev Prabhakar², Norito Takenaka¹

Affiliations

¹ Department of Chemistry and Chemical Engineering, Florida Institute of Technology, 150 West University Boulevard, Melbourne, Florida 32901-6975, USA.
² Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, Florida 33146-0431, USA.

Abstract

Distilled propargyltrichlorosilane with >99% isomeric purity was prepared for the first time, and its asymmetric catalytic regiospecific addition reaction to aldehydes was developed through a systematic catalyst structure-reactivity and selectivity relationship study. The observed catalyst structure-enantioselectivity relationship of the present allenylation reaction was found exactly opposite to that of the analogous allylation reaction. The method provided eleven α-allenic alcohols in 22-99% yield with 61:39-92:8 enantiomeric ratios. Furthermore, possible mechanisms of propargyl-allenyl isomerization of propargyltrichlorosilane were computationally investigated.

Keywords: Lewis base catalysis; computational chemistry; organocatalysis; propargyltrichlorosilane; α-allenic alcohol.

Grants and funding

This work was financially supported by a grant from the National Institute of Health (1R15 GM139087-01) to N.T. and a grant from the National Science Foundation (Grant Number CHE- 2102563) to R.P.