Del Grosso Alessandro, Chamberlain Alexander E, Clarkson Guy J, Wills Martin
Department of Chemistry, The University of Warwick, Coventry, CV4 7AL, UK.
Dalton Trans. 2018 Jan 30;47(5):1451-1470. doi: 10.1039/c7dt03250a.
A series of cyclopentadienone iron tricarbonyl complexes with diverse structures were prepared, in each case using the intramolecular cyclisation of a diyne as a key step. The complexes were generated as enantiomerically enriched through (i) asymmetric synthesis of a C2-symmetric diol following a reported protocol, (ii) resolution of enantiomerically-enriched diastereoisomers formed from a chiral alcohol and (iii) kinetic resolution of a racemic ketone-containing iron tricarbonyl complex. The approaches underline the diversity of the synthetic routes which can be employed in the synthesis of homochiral cyclopentadienone iron tricarbonyl complexes. Although the complexes proved to be effective as catalysts for the reduction of ketones, the alcohol products were formed in low ees (not exceeding ca. 35%), highlighting the challenging nature of asymmetric catalysis using complexes of this type.
制备了一系列结构各异的环戊二烯酮三羰基铁配合物，每种情况均以二炔的分子内环化作为关键步骤。这些配合物通过以下方式生成对映体富集产物：(i) 按照报道的方案不对称合成C2对称二醇；(ii) 拆分由手性醇形成的对映体富集非对映异构体；(iii) 动力学拆分含外消旋酮的三羰基铁配合物。这些方法突显了可用于合成手性环戊二烯酮三羰基铁配合物的合成路线的多样性。尽管这些配合物被证明是有效的酮还原催化剂，但醇产物的对映体过量值较低（不超过约35%），这突出了使用此类配合物进行不对称催化的挑战性。
