Enantioenriched Molybdenum Dearomatization: Dissociative Substitution with Configurational Stability
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https://figshare.com/articles/dataset/Enantioenriched_Molybdenum_Dearomatization_Dissociative_Substitution_with_Configurational_Stability/5964940
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资源简介：
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.
创建时间：
2018-05-25
