Palladium-Catalyzed Carboxylation of Allyl Stannanes and Carboxylative Coupling of Allyl Stannanes and Allyl Halides [Abstract]

Authors

Russell J. Franks, Stephen F Austin State UniversityFollow

Document Type

Conference Proceeding

Publication Date

1998

Abstract

The reaction of allyl stannanes with CO₂ to form stannyl carboxylates (esters) is catalyzed by Pd(PR₃)₄ complexes. Thus, R₃SnCH₂CH=CH₂ [R=Me and Ph]are converted to R₃SnO₂ CCH₂CH=CH₂ and R₃SnO₂CCH=CHCH₃ under 33 atm of CO₂ (70°C, THF) in moderate to excellent yield in the presence of 8 mol% Pd(PPh₃)₄ ; polycarboxylation of diallyldibutyltin and tetraallyltin also is effected, producing the respective di- and tetracarboxylates, Bu₂Sn(O₂CCH₂CH=CH₂)₂ and Sn(O₂CCH₂ CH=CH₂)₄ , along with the corresponding isomeric crotyl derivatives. In the presence of allyl halides, allyl stannanes and CO₂ undergo carboxylative coupling to produce allyl esters. Under these conditions other Sn-C (Sn-alkyl, -aryl, -vinyl) and Si-C (Si-allyl, -alkyl, -aryl, -vinyl) bonds are inert to carboxylation and carboxylative coupling with allyl halides. A tentative mechanism is proposed to account for this catalytic carboxylation of a main group metal-carbon bond.

Repository Citation

Franks, Russell J., "Palladium-Catalyzed Carboxylation of Allyl Stannanes and Carboxylative Coupling of Allyl Stannanes and Allyl Halides [Abstract]" (1998). Faculty Publications. 31.
https://scholarworks.sfasu.edu/chemistry_facultypubs/31