ABSTRACT
The current investigation presents an innovative palladium-catalyzed asymmetric carbonylative Heck esterification method. This approach facilitates the efficient synthesis of various chiral γ-ketoacid esters by utilizing o-alkenyliodobenzenes and arylboronic acids as primary substrates. This reaction achieves the creation of three carbon-carbon bonds, two carbon-oxygen bonds, and the establishment of a quaternary carbon center within a single step. The α-chiral γ-ketoacid esters were obtained in yields ranging from good to high yields, displaying enantiomeric excesses (ee's) levels up to 92% under mild reaction conditions.
ABSTRACT
Activation and cleavage of carbon-carbon (C-C) bonds is a fundamental transformation in organic chemistry while inert C-C bonds cleavage remains a long-standing challenge. Retro-Diels-Alder (retro-DA) reaction is a well-known and important tool for C-C bonds cleavage but less been explored in methodology by contrast to other strategies. Herein, we report a selective C(alkyl)-C(vinyl) bond cleavage strategy realized through the transient directing group mediated retro-Diels-Alder reaction of a six-membered palladacycle, which is obtained from an in situ generated hydrazone and palladium hydride species. This unprecedented strategy exhibits good tolerances and thus offers new opportunities for late-stage modifications of complex molecules. DFT calculations revealed that an intriguing retro-Pd(IV)-Diels-Alder process is possibly involved in the catalytic cycle, thus bridging both Retro-Diels-Alder reaction and C-C bond cleavage. We anticipate that this strategy should prove instrumental for potential applications to achieve the modification of functional organic skeletons in synthetic chemistry and other fields involving in molecular editing.
