Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China.
Chemistry. 2010 Sep 3;16(33):10124-9. doi: 10.1002/chem.201000284.
An easily available and efficient chiral N,N'-dioxide-nickel(II) complex catalyst has been developed for the direct catalytic asymmetric aldol reaction of alpha-isothiocyanato imide with aldehydes which produces the products in morderate to high yields (up to 98 %) with excellent diastereo- (up to >99:1 d.r.) and enantioselectivities (up to >99 % ee). A variety of aromatic, heteroaromatic, alpha,beta-unsaturated, and aliphatic aldehydes were found to be suitable substrates in the presence of 2.5 mol % L-proline-derived N,N'-dioxide L5-nickel(II) complex. This process was air-tolerant and easily manipulated with available reagents. Based on experimental investigations, a possible transition state has been proposed to explain the origin of reactivity and asymmetric inductivity.
已开发出一种易得且高效的手性 N,N'-二氧化氮-镍(II)配合物催化剂,用于α-异硫氰酸亚胺与醛的直接催化不对称羟醛反应,产物的收率中等至高产(高达 98%),具有优异的非对映选择性(高达>99:1 d.r.)和对映选择性(高达>99%ee)。在 2.5 mol% L-脯氨酸衍生的 N,N'-二氧化氮 L5-镍(II)配合物的存在下,发现各种芳香族、杂芳族、α,β-不饱和和脂肪族醛都是合适的底物。该过程对空气具有耐受性,并且可以使用现有试剂轻松操作。基于实验研究,提出了一种可能的过渡态,以解释反应性和不对称诱导性的起源。