Cyclic beta-diketones - Precursors of chiral 1,3-cyclohexadiene iron carbonyl complexes. Ligand exchange - (-)-PPh(2)(O-HC(Me)-COOEt) - New, chiral, diastereomer-separating ligand in organoiron chemistry
Cyclic beta-diketones - Precursors of chiral 1,3-cyclohexadiene iron carbonyl complexes. Ligand exchange - (-)-PPh(2)(O-HC(Me)-COOEt) - New, chiral, diastereomer-separating ligand in organoiron chemistry
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DOI：
10.1016/0022-328x(95)05761-d
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发表时间：
1996-01-25
影响因子：
2.3
通讯作者：
Hutta, M
中科院分区：
文献类型：
--
作者：
Bohac, A;Lettrichova, M;Hutta, M
以1，3-环己二酮和5，5-二甲基-1，3-环己二酮（二甲酮）为原料，经转化为1，3-二乙酰氧基-1，3-环己二烯，再与Fe-2（CO）（9）络合，合成了新的手性三羰基铁配合物（1，2）。配合物1，2分别与PPh（3）（A），（-）-P（O-HC*（Me）-COOEt）（3 ′-（-）-TEOCEOP ′（B）和（-）-PPh（2）（O-HC*（Me）-COOEt）′ LACTODIPPHOS ′（C）进行了配体交换反应。从市售的（S）-（-）乳酸乙酯（-）-PPh，（O-HC*（Me）-COOEt）（C）中发现了一种新的具有应用前景的手性配体，并成功地分离了（1，3-二乙酰氧基-1，3-环己二烯）Fe（CO）（2）PPh（2）（O-HC*（Me）-COOEt）配合物1C（1C（120）和1C（160））的非对映异构体混合物。
A synthesis of new, chiral tricarbonyliron complexes (1, 2) from 1,3-cyclohexanedione and 5,5-dimethyl-1,3-cyclohexanedione (dimedone) after their conversion to 1,3-diacetoxy-1,3-cyclohexadienes and complexation with Fe-2(CO)(9) is described. Ligand-exchange reactions of complexes 1,2 with PPh(3) (A), (-)-P(O-HC*(Me)-COOEt)(3)'(-)-TEOCEOP' (B) and (-)-PPh(2)(O-HC*(Me)-COOEt) 'LACTODIPPHOS' (C) were accomplished in good yield. A new prospective chiral ligand for organoiron chemistry, derived from commercially available (S)-(-)ethyl lactate, (-)-PPh,(O-HC*(Me)-COOEt) (C) was found. By means of ligand C, a diastereoisomeric mixture of the (1,3-diacetoxy-1,3-cyclohexadiene)Fe(CO)(2)PPh(2)(O-HC*(Me)-COOEt) complex 1C (1C(120) and 1C(160)) was successfully separated.