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- W2791840247 abstract "The preparation and properties of the complex (RMo,R)-MoTp(NO)(DMAP)(η2-α-pinene) are described (∼10 g scale; DMAP = 4-(dimethylamino)pyridine; Tp = hydridotris(pyrazolyl)borate). This complex undergoes exchange of the pinene with a wide range of other π ligands including acetone, ethyl acetate, N,N-dimethylformamide, acetonitrile, and naphthalene. Treatment of the α-pinene complex with iodine results in the complex (S)-MoTp(NO)(DMAP)(I), which is recovered in enantioenriched form (er = 99:1; yield >90%; scale 4.6 g). Reduction of this molybdenum(I) precursor results in enantioenriched molybdenum(0) complexes, including (R)-MoTp(NO)(DMAP)(η2-trifluorotoluene). Sequential treatment of this arene complex with acid, a masked enolate, and iodine regenerates MoTp(NO)(DMAP)(I) along with an alkylated 1-(trifluoromethyl)cyclohexa-1,3-diene with an er value as high as 99:1. This process demonstrates the efficient transfer of asymmetry from α-pinene to the diene product. Accompanying studies with (1R)-myrtenal reveal a redox-catalyzed pinene/myrtenal ligand exchange occurring through Mo(I) intermediates." @default.
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- W2791840247 date "2018-03-08" @default.
- W2791840247 modified "2023-10-01" @default.
- W2791840247 title "Enantioenriched Molybdenum Dearomatization: Dissociative Substitution with Configurational Stability" @default.
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- W2791840247 doi "https://doi.org/10.1021/acs.organomet.8b00027" @default.
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