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Two Catalytic Annulation Modes via Cu-Allenylidenes with Sulfur Ylides that Are Dominated by the Presence or Absence of Trifluoromethyl Substituents.

ABSTRACT: We disclose the Cu-catalyzed enantioselective synthesis of 3-methyl-3-propargyl-indolines, which contain a quaternary stereogenic carbon center, via the decarboxylative [4 + 1] annulation of 4-methyl-4-propargyl-benzoxazinanones with variety of sulfur ylides. The reaction proceeds predominantly through a ?-attack at the Cu-allenylidene intermediates by sulfur ylides to provide the corresponding indolines in good yield and high enantioselectivity (up to 91% ee). In contrast, the reaction of 4-trifluoromethyl-4-propargyl-benzoxazinanones with sulfur ylides delivers 3-trifluoromethyl-2-functionalized indoles in good to high yield via an unexpected ?-attack at the Cu-allenylidene intermediates. Control over the ?/?-attack at the Cu-allenylidene intermediates by the same interceptors was achieved for the first time by the use of trifluoromethyl substituents.

SUBMITTER: Gannarapu MR

PROVIDER: S-EPMC7132161 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Two Catalytic Annulation Modes via Cu-Allenylidenes with Sulfur Ylides that Are Dominated by the Presence or Absence of Trifluoromethyl Substituents.

Gannarapu Malla Reddy MR Zhou Jun J Jiang Bingyao B Shibata Norio N

iScience 20200320 4

We disclose the Cu-catalyzed enantioselective synthesis of 3-methyl-3-propargyl-indolines, which contain a quaternary stereogenic carbon center, via the decarboxylative [4 + 1] annulation of 4-methyl-4-propargyl-benzoxazinanones with variety of sulfur ylides. The reaction proceeds predominantly through a γ-attack at the Cu-allenylidene intermediates by sulfur ylides to provide the corresponding indolines in good yield and high enantioselectivity (up to 91% ee). In contrast, the reaction of 4-tri ...[more]

PMID: 32259670

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