Reactivity and Utility of Allenylphosphonates: Formation of a Novel Hydroperoxide and Propargylic Alcohol and Facile Thiol Addition under Catalyst-Free, Solvent-Free Conditions

Manab Chakravarty; K. C. Kumara Swamy

doi:10.1055/s-2007-990794

PAPER

Reactivity and Utility of Allenylphosphonates: Formation of a Novel Hydroperoxide and Propargylic Alcohol and Facile Thiol Addition under Catalyst-Free, Solvent-Free Conditions

Manab Chakravarty, K. C. Kumara Swamy*
School of Chemistry, University of Hyderabad, Hyderabad 500046, AP, India
Fax: +91(40)23012460; e-Mail: kckssc@uohyd.ernet.in;

Abstract

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Abstract

2-(Propa-1,2-dienyl)-, 2-(buta-1,2-dienyl)-, and 2-(3-methylbuta-1,2-dienyl)-substituted 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 1a-c react readily upon heating with thiols under catalyst-free, base-free, and solvent-free conditions to give sulfanyl-substituted phosphonates. The reaction undergoes to essential completion within 15 minutes under microwave radiation. While 1a,b react with 4-chlorothiophenol to afford both 2-[2-(4-chlorophenylsulfanyl)prop-1-enyl]- 12 and 2-[2-(4-chlorophenylsulfanyl)prop-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 13, 1c gives 2-[2-(4-chlorophenylsulfanyl)-3-methylbut-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (13d) regioselectively. Molecular oxygen undergoes a novel reaction with the allene 1c to give propargylic alcohol 2-(3-hydroxy-3-methylbut-1-ynyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (16) via the corresponding hydroperoxide; the structures of these were confirmed by X-ray crystallography. The synthetic utility of the sulfanyl-substituted allyphosphonate 13d in the Horner-Wadsworth-Emmons reaction to afford synthetically valuable sulfanyl-substituted buta-1,3-dienes and a conjugated triene is demonstrated.

Key words

allenes - thiol addition - oxygenation - Horner-Wadsworth-Emmons reaction - allenylphosphonates

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References

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