Enantioenriched Molybdenum Dearomatization: Dissociative Substitution with Configurational Stability
Organometallics(2018)
摘要
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.
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关键词
dissociative substitution
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