Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds.

Element−Element Addition to Alkynes Catalyzed by the Group 10 Metals

Platinum(II)-catalyzed 1,6-diene cycloisomerizations: Turnover in the absence of β-hydride elimination

Thermodynamics of the Metal–Hydrogen Bonds in (η5-C5H5)M(CO)2H (M = Fe, Ru, Os)

The reaction of (Z)-HDCCHCH(OCH3)C6H5 (1) with Cp2Zr(D)Cl followed by BF3·OEt2 gave phenylcyclopropanes 3a and 3b, both having cis deuterium. This stereochemical outcome requires inversion of configuration at the carbon bound to zirconium and is consistent with a “W-shaped” transition state structure for cyclopropane formation. In a Kulinkovich hydroxycyclopropanation, trans-3-deutero-1-methyl-cis-2-phenyl-1-cyclopropanol (5) was formed stereospecifically from Ti(O-i-Pr)4, ethyl acetate, EtMgBr, and trans-β-deuterostyrene. This stereochemistry requires retention of configuration at the carbon bound to titanium and is consistent with frontside attack of the carbon−titanium bond on a carbonyl group coordinated to titanium. In a de Meijere cyclopropylamine synthesis, a 3:1 mixture of N,N-dimethyl-N-(trans-3-deutero-trans-2-phenylcyclopropyl)amine (6a) and N,N-dimethyl-N-(cis-3-deutero-cis-2-phenylcyclopropyl)amine (6b) was formed from Ti(O-i-Pr)4, DMF, Grignard reagents, and trans-β-deuterostyrene. This ster...

Laura J. Smith

Papers

Cyclopropane formation from the reaction of (.gamma.-haloalkyl)iron compounds with silver(1+)

Inversion of stereochemistry at the carbon bound to iron in cyclopropane formation from threo-C5H5(CO)2FeCHDCHDCH2S(CH3)C6H5+