A series of mono- and di-substituted allenes underwent direct thiocarbonylation with thiols and carbon monoxide to form the corresponding β,γ-unsatd. thioesters in 73-94% yields. This reaction requires catalytic quantities of Pd(OAc)2 (3 mol %) and triphenylphosphine (12 mol %) in THF under an atm. of CO (400 psi) at 100 °C for 48 h. Other palladium catalyst systems such as Pd2(dba)3·CHCl3-PPh3, Pd(PPh3)4, and Pd(OAc)2-dppp are also effective for this reaction. The thiocarbonylation reaction is believed to proceed via an allylpalladium intermediate. The reaction exhibits high regioselectivity, in which the thiophenyl group adds to the less substituted double bond of allenes to give β,γ-unsatd. thioesters.

Highly Regioselective Palladium -Catalyzed Thiocarbonylation of Allenes With Thiols and Carbon Monoxide

VASAPOLLO, Giuseppe;
1998

Abstract

A series of mono- and di-substituted allenes underwent direct thiocarbonylation with thiols and carbon monoxide to form the corresponding β,γ-unsatd. thioesters in 73-94% yields. This reaction requires catalytic quantities of Pd(OAc)2 (3 mol %) and triphenylphosphine (12 mol %) in THF under an atm. of CO (400 psi) at 100 °C for 48 h. Other palladium catalyst systems such as Pd2(dba)3·CHCl3-PPh3, Pd(PPh3)4, and Pd(OAc)2-dppp are also effective for this reaction. The thiocarbonylation reaction is believed to proceed via an allylpalladium intermediate. The reaction exhibits high regioselectivity, in which the thiophenyl group adds to the less substituted double bond of allenes to give β,γ-unsatd. thioesters.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11587/111725
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