Quaternary carbon stereocenters–carbon atoms bonded to four distinct carbon substituents–are found in many biologically active molecule natural products. In the past few decades, stereoselective synthesis has played a crucial role in organic chemistry, leading to the rapid development of many powerful methods for stereocontrolled construction of various chiral organic molecules that the stereocenters contain one hydrogen substituent. In marked contrast, the stereoselective construction of all-carbon quaternary stereocenters remains as a formidable challenge for synthetic organic chemists. One of the difficulties in constructing quaternary carbons is their congested nature. Besides the challenge of steric hindrance, the stereoselective construction of all-carbon quaternary stereocenters requires the use of asymmetric C–C bond forming reactions that are far less than well-established asymmetric oxidation and reduction reactions. To address this challenge, we describe an efficient approach that involves the formation of two new stereogenic centers, including one all-carbon quaternary carbon stereocenter, via a cascade intermolecular–intramolecular asymmetric carbometalation process of dienes. This new approach provides a rapid access to a variety of chiral compounds bearing an all-carbon quaternary stereocenter in highly regio- and stereoselective manner. Moreover, its application to the synthesis of bioactive and medicinally important natural products will be discussed.

Stereo- and enantioselective synthesis of chiral compounds bearing an all-carbon quaternary stereocenter by ZACA reaction

253rd National Meeting (2017)

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