Kyoto Pharmaceutical University , Yamashina, Kyoto 607-8412, Japan.
J Org Chem. 2013 Nov 1;78(21):10986-95. doi: 10.1021/jo401893f. Epub 2013 Oct 23.
Gold(I)-catalyzed asymmetric intramolecular cyclization of prochiral 1,3-dihydroxymethyl-2-alkynylbenzene or 1,3-bis(carbamate)-2-alkynylbenzene tricarbonylchromium complexes with axially chiral diphosphine ligand gave planar chiral tricarbonylchromium complexes of 1H-isochromene or 1,2-dihydroisoquinoline with high enantioselectivity. An enantiomeric excess of the planar chiral arene chromium complexes was largely affected by a combination of axially chiral diphosphine(AuCl)2 precatalysts and silver salts. In the case of 1,3-dihydroxymethyl-2-alkynylbenzene chromium complexes, a system of segphos(AuCl)2 with AgBF4 resulted in the formation of the corresponding antipode.
金(I)催化的前手性 1,3-二羟甲基-2-炔基苯或 1,3-双(氨基甲酸酯)-2-炔基苯三羰基铬配合物与轴向手性双膦配体的不对称分子内环化反应,得到具有高对映选择性的 1H-异色烯或 1,2-二氢异喹啉的平面手性三羰基铬配合物。平面手性芳烃铬配合物的对映过量主要受轴向手性双膦(AuCl)2 前催化剂和银盐的组合影响。在 1,3-二羟甲基-2-炔基苯铬配合物的情况下,segphos(AuCl)2 与 AgBF4 的体系导致相应对映体的形成。