Diastereoselective synthesis of C2-symmetric hexacoordinated phosphate anions (HYPHATs) with predetermined chirality from 1,2-diaryl-ethane-1,2-diols
摘要:
C-symmetric HYPHAT anion (5) made of a central phosphorus(V) atom. one hydrobenzoin and two tetracholorocatechol ligands can be simply prepared in high yield as its dimethylammonium salt using a one pot-process and simple commercially available or easily prepared starting materials. The presence of the chiral hydrobenzoin ligands (e.g. R,R) leads to the formation of diastereomeric anions (Delta.R.R/A.R.R). A partial control over the configuration of the adduct by the chiral ligands is observed (diastereomeric ratio (d.r.) 75:25 in 5% DMSO-CHCl3). This asymmetric induction can be improved (d.r. up to 90:10) by the introduction of ortho bromo substituents on the phenyl rings of the 1,2-diaryl-ethane-1,2-diol ligands. (C) 2002 Elsevier Science B,V. All rights reserved.
探索了基于新型双(茚基)-( E / Z )-二苯乙烯平台的二锆配合物的制备。由各自的o / m / p -( E / Z )-二溴芪和溴官能化锆茂(η 5 -Cp*)(η 5 -2-甲基-4-溴茚基)获得的原位生成的二有机锌酸盐之间的Negishi偶联)ZrCl 2 ,或者,通过相应的二溴二苯乙烯与4-溴茚的Negishi偶联和随后的金属化来制备双(茚)二苯乙烯前配体{ o / m / p -( E / Z )-BisIndSB}H 2与Cp*ZrCl 3或Zr(NMe 2 ) 4的金属转移可以制备一系列双核配合物。这些通过核磁共振波谱法进行分析,其中一些通过 iASAP 质谱法和 X 射线衍射研究进行分析。将实验结果与目标双核配合物的 DFT 模型进行比较,证明 ( E )-配合物比其 ( Z )-类似物稳定 7-11 kcal mol -1 。在某些系统的合成过程中,通过实验观察到(
Diastereoselective synthesis of C2-symmetric hexacoordinated phosphate anions (HYPHATs) with predetermined chirality from 1,2-diaryl-ethane-1,2-diols
作者:Jérôme Lacour、Anne Londez
DOI:10.1016/s0022-328x(01)01251-7
日期:2002.2
C-symmetric HYPHAT anion (5) made of a central phosphorus(V) atom. one hydrobenzoin and two tetracholorocatechol ligands can be simply prepared in high yield as its dimethylammonium salt using a one pot-process and simple commercially available or easily prepared starting materials. The presence of the chiral hydrobenzoin ligands (e.g. R,R) leads to the formation of diastereomeric anions (Delta.R.R/A.R.R). A partial control over the configuration of the adduct by the chiral ligands is observed (diastereomeric ratio (d.r.) 75:25 in 5% DMSO-CHCl3). This asymmetric induction can be improved (d.r. up to 90:10) by the introduction of ortho bromo substituents on the phenyl rings of the 1,2-diaryl-ethane-1,2-diol ligands. (C) 2002 Elsevier Science B,V. All rights reserved.
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