期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 32, 页码 12622-12632出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c05087
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资金
- Shanghai Sailing Program [19YF1421900]
- Shanghai Municipal Education Commission [201701070002E00030]
- Science and Technology Commission of Shanghai Municipality [19JC1430100]
- National Natural Science Foundation of China [21690063, 21831005, 21901158, 21991112]
This study presents a method for the construction of 1,3-nonadjacent stereocenters through Pd/Cu-catalyzed asymmetric synthesis, providing highly enantio- and diastereoselective chiral products; The protocol is applicable to a wide range of substrates, including challenging allenylic esters with less sterically bulky substituents; Moreover, various transformations involving axial-to-central chirality transfer were conducted, yielding useful structural motifs containing nonadjacent stereocenters in a diastereodivergent manner.
In contrast to the widely explored methods for the asymmetric synthesis of molecules bearing a single stereocenter or adjacent stereocenters, the concurrent construction of 1,3-stereogenic centers in an enantio- and diastereoselective manner remains a challenge, especially in acyclic systems. Herein, we report an enantio- and diastereodivergent construction of 1,3-nonadjacent stereocenters bearing allenyl axial and central chirality through synergistic Pd/Cu-catalyzed dynamic kinetic asymmetric allenylation with racemic allenylic esters. The protocol is suitable for a wide range of substrates including the challenging allenylic esters with less sterically bulky substituents and provided chiral allenylic products bearing 1,3-nonadjacent stereocenters with high levels of enantio- and diastereoselectivities (up to >20:1 dr and >99% ee). Furthermore, several representative transformations involving axial-to-central chirality transfer were conducted, affording useful structural motifs containing nonadjacent stereocenters in a diastereodivergent manner.
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