Mechanistic Investigation of the Asymmetric Addition of Trimethylsilyl Cyanide to Aldehydes Catalysed by Dinuclear Chiral (Salen)titanium Complexes

Mechanistic Investigation of the Asymmetric Addition of Trimethylsilyl Cyanide to Aldehydes Catalysed by Dinuclear Chiral (Salen)titanium Complexes
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DOI:
10.1002/1099-0690(200007)2000:14
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发表时间:
2000-07
影响因子:
2.8
通讯作者:
Y. Belokon’;B. Green;N. Ikonnikov;V. Larichev;B. Lokshin;M. A. Moscalenko;M. North;C. Orizu;A. Peregudov;Galina I. Timofeeva
Y. Belokon’;B. Green;N. Ikonnikov;V. Larichev;B. Lokshin;M. A. Moscalenko;M. North;C. Orizu;A. Peregudov;Galina I. Timofeeva
中科院分区:
化学3区
文献类型:
--
作者:
Y. Belokon’;B. Green;N. Ikonnikov;V. Larichev;B. Lokshin;M. A. Moscalenko;M. North;C. Orizu;A. Peregudov;Galina I. Timofeeva

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手性salen配体衍生的钛配合物1是三甲基硅腈对醛酮不对称加成反应的高活性预催化剂。基于光谱研究和配合物1和羰基化合物或三甲基甲硅烷基氰化物之间的加合物的鉴定,提出了一个催化循环,解释了起源的不对称诱导。动力学研究已经进行,其结果是一致的,建议的催化循环。
Titanium complexes 1 derived from chiral salen ligands are highly active precatalysts for the asymmetric addition of trimethylsilyl cyanide to aldehydes and ketones. Based on spectroscopic studies and the identification of adducts between complexes 1 and carbonyl compounds or trimethylsilyl cyanide, a catalytic cycle which explains the origin of the asymmetric induction is proposed. Kinetics studies have been carried out, the results of which are consistent with the proposed catalytic cycle.