A new facile synthesis of 2-substituted 1,3-butadiene derivatives via palladium-catalyzed cross-coupling reaction of 2,3-alkadienyl carbonates with organoboron compounds

✍ Scribed by Tsukasa Moriya; Toshinari Furuuchi; Norio Miyaura; Akira Suzuki

• Publisher: Elsevier Science
• Year: 1994
• Tongue: French
• Weight: 447 KB
• Volume: 50
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)85281-9

✦ Synopsis

A synthesis of 2-aryl-. 2-(1-alkenyl)-, and 2-alkyl-1,3-butadiene derivatives (2) by the palladiumcatalyzed cross-coupling reaction of 2,3-bumiienyl carbonatea (1) with 9-alkyl-9-bicyclo[3.3.llmman~ (9-alkyl-9-BBN), 1-aknylboronic acids, or arylbcmdc acids is described. The reaction pmeeded regiosekctively with the palhlium-pba3pldne complexes under neutral conditions.

The palladium-catalyzed carbonylation and coupling reactions of allylic, propargylic, and 2,3alkadienyl carbonates have been extensively studied by Tsuji and Mandai.1 The reaction provides an efficient method for in situ generation of an (alkoxo)palladium(II) species by oxidative addition of the carbonates to Pd(0) complex, and their addition and coupling with electrophiles have enabled various synthetic transformations which are not accessible by the conventional methods. Although these carbonates are also attractive as a substrate for the cross-coupling reaction with organometallic reagents, such reaction has not been reported to date.