Highly Enantioselective Cyclocarbonylation of Allylic Alcohols Catalyzed by Novel Pd-1,4-bisphosphine Complexes

Transition metal-catalyzed carbonylation reactions are fundamentally important organic transformations.1,3 Despite the great potential of asymmetric carbonylation reactions and the extensive effort devoted to this reaction during the last several decades,4 only moderate success ( 1,3-bisphosphine . 1,2bisphosphine. The high catalytic reactivity the Pd-catalyzed carbonylation with a 1,4-bisphosphine ligand is associated with a relatively flexible ligand-metal seven-membered ring chelate. Since BICP is one of the most effective chiral 1,4-bisphosphines, we chose to evaluate this ligand as it might meet the two primary requirements for achieving high enantioselectivity and activity in Pd-catalyzed cyclocarbonylation reactions: (1) conformational rigidity of Pd-bisphosphine complexes conducive to chiral induction and (2) a relatively flexible seven-membered ligandmetal chelate favorable for rapid CO insertion. We selected 3,3-dimethyl-2-phenyl propenol (1a) as the initial substrate for study. Several experiments have been conducted to identify CH2Cl2 under a CO/H2 atmosphere (total pressure ) 800 psi, ratio of CO/H2 ) 1:1) at 80 °C with 1 mol % of Pd-catalyst(Table 1). The Pd-BICP catalyst was prepared in situ from Pd2(dba)3 and (R,R)-BICP. Under these conditions, cyclocarbonylation of 1a gave product 2a in 95%ee (entry 1). When Xyl-BICP was examined under the same reaction conditions, lactone 2a was generated in 95% ee and 87% yield (entry 2). To the best of our knowledge, this is the highest enantioselectivity reported to date for the cyclocarbonylation of 2-methyl-3-phenyl3-buten-2-ol. In a related study, Alper et al.6e reported an 81% ee for cyclocarbonylation of 1a using a Pd-BPPM catalyst, whereas 45% ee and 31% ee were obtained with Pd-DIOP and Pd-BINAP catalysts, respectively. No cyclocarbonylation of 1a occurred when DuPhos and CHIRAPHOS were used as the chiral ligands. 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