113158-94-4Relevant articles and documents
Diastereoselective arbuzov dealkylation and evidence for phosphorus-carbon bond activation of prochiral cobalt(III) phosphonite complexes
Boone, Brian J.,Jablonski, Chet R.,Jones, Peter G.,Newlands, Michael J.,Yu, Yongfei
, p. 3042 - 3050 (1993)
(Sc)-(η5-Cp)CoI2(PPh 2NHC*H(Me)Ph) reacts with 1 equiv of dimethyl tert-butyl- or ethylphosphonite in methylene chloride solution to give diastereomeric P-chiral phosphinate Arbuzov products (R,SCo;RP;SC)-(η 5-Cp)CoI(PPh2NHC*H(Me)Ph)(P(0)(OMe)(t-Bu)) (3a) and (R,SCo;R,SP;SC)-(η 5-Cp)CoI(PPh2NHC*H(Me)Ph)(P(O)(OMe)(Et)) (3b), respectively. Apparent phosphorus-carbon bond cleavage also occurs to give (R,SCo;SC)-(η5-Cp)CoI(PPh 2NHC*H(Me)Ph)(P(O)(OMe)2) (4), which was isolated in low yield after aerial workup. Two diastereomers of the tert-butyl series 3a and one diastereomer of the four isolated for the ethyl series 3b were characterized by single-crystal X-ray diffraction. (SCo;RP;SC)-3a-1 crystallizes in the space group P212121 with a = 9.815(4) A?, b = 14.314(6) A?, c = 21.120(9) A?, V = 2967(2) A?3, Z = 4, and RF = 2.83% for 5958 reflections (F > 4.0σ(F)) at 198 K. (ACo;SP;SC)-3a-2 crystallizes in the space group P21 with a = 13.073(5) A?, b = 8.731(2) A?, c = 13.537(5) A?, β = 106.49(3)°, V = 1481.5(9) A?3, Z = 2, and RF = 3.19% for 4846 reflections (F > 4.0σ(F)) at 198 K. (RCo;SP;SC)-3b-2 crystallizes in the space group P212121 with a = 8.7004(7) A?, b = 12.0769(18) A?, c = 27.490(3) A?, V = 2888.5(6) A?3, Z = 4, and RF = 4.4% for 3118 reflections (F > 2.5σ(F)) at 297 K. The absolute configurations of all diastereomers were assigned on the basis of crystallographic results, circular dichroism, and chemical cycles involving Co epimerization. P=O?H-N intramolecular hydrogen bonding establishes a chaise longue conformation with pseudoaxial η5-Cp and pseudoequatorial iodide in the solid state. Proton nuclear Overhauser difference (NOED) spectra show that the solid-state conformation is retained in solution. Optical yields increased with increasing steric demands of the prochiral phosphonite substituent. A model based on 1,3-diaxial steric interactions in the transition state leading to dealkylation is proposed to account for the observed Co→P chiral induction.