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Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes.

ABSTRACT: Metal-catalyzed enantioselective construction of the loosening axial allene chirality spreading over three carbon atoms using a chiral ligand is still a significant challenge. In the literature, steric effect of the substrates is the major strategy applied for such a purpose. Herein, we present a general palladium-catalyzed asymmetrization of readily available racemic 2,3-allenylic carbonates with different types of non-substituted and 2-substituted malonates using (R)-(-)-DTBM-SEGPHOS as the preferred ligand to afford 1,3-disubstituted chiral allenes with 90~96% ee. This protocol has been applied to the first enantioselective synthesis of natural product, (R)-traumatic lactone. Control experiments showed that in addition to the chiral ligand, conducting this transformation via Procedure C, which excludes the extensive prior coordination of the allene unit in the starting allene with Pd forming a species without the influence of the chiral ligand, is crucial for the observed high enantioselectivity.

SUBMITTER: Song S

PROVIDER: S-EPMC6355870 | biostudies-other | 2019 Jan

REPOSITORIES: biostudies-other

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Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes.

Song Shihua S Zhou Jing J Fu Chunling C Ma Shengming S

Nature communications 20190131 1

Metal-catalyzed enantioselective construction of the loosening axial allene chirality spreading over three carbon atoms using a chiral ligand is still a significant challenge. In the literature, steric effect of the substrates is the major strategy applied for such a purpose. Herein, we present a general palladium-catalyzed asymmetrization of readily available racemic 2,3-allenylic carbonates with different types of non-substituted and 2-substituted malonates using (R)-(-)-DTBM-SEGPHOS as the pr ...[more]

PMID: 30705274

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