Enantioenriched Molybdenum Dearomatization: Dissociative Substitution with Configurational Stability,Organometallics

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Enantioenriched Molybdenum Dearomatization: Dissociative Substitution with Configurational Stability
Organometallics ( IF 2.5 ) Pub Date : 2018-03-08 , DOI: 10.1021/acs.organomet.8b00027
Philip J. Shivokevich ₁ , Jeffery T. Myers ₁ , Jacob A. Smith ₁ , Jared A. Pienkos ₁ , Steven J. Dakermanji ₁ , Emmit K. Pert ₁ , Kevin D. Welch ₁ , Carl O. Trindle ₁ , W. Dean Harman ₁

Affiliation

The preparation and properties of the complex (R_Mo,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.

中文翻译：

对映体富集的钼脱芳香化：具有构型稳定性的解离取代

该复合体（的制备和性能- [R_沫，R）-MoTp（NO）吡啶（DMAP）（η ²- α蒎烯）中有所描述（〜10克规模; DMAP = 4-（二甲基氨基）吡啶; TP =氢化三（吡唑基）硼酸盐）。该配合物经历the烯与广泛范围的其他π配体的交换，所述其他π配体包括丙酮，乙酸乙酯，N，N-二甲基甲酰胺，乙腈和萘。用碘处理α- pine烯络合物会生成（S）-MoTp（NO）（DMAP）（I）络合物，以对映体富集的形式回收（er = 99：1;收率> 90％;规模4.6 g）。此钼（I）前体导致对映体富集的钼减少（0）配合物，包括：（[R）-MoTp（NO）吡啶（DMAP）（η ²-三氟甲苯）。依次用酸，被掩盖的烯醇化物和碘对该芳烃配合物进行处理，可以使MoTp（NO）（DMAP）（I）与er值高达99的烷基化的1-（三氟甲基）环己-1,3-二烯一起再生：1。该过程证明了不对称性从α-pine烯到二烯产物的有效转移。与（1 R）-myrtenal的伴随研究表明通过Mo（I）中间体发生氧化还原催化的ligand烯/ myrtenal配体交换。

更新日期：2018-11-29

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