Rotational isomerization of 3-substituents in synthetic chlorophyll derivatives

被引：11
作者：
Tamiaki, Hitoshi [1 ]
Mizutani, Keisuke [1 ]
Sasaki, Shin-ichi [1 ,2 ]
Tatebe, Tomohiro [1 ]
机构：
[1] Ritsumeikan Univ, Grad Sch Life Sci, Kusatsu, Shiga 5258577, Japan
[2] Nagahama Inst Biosci & Technol, Nagahama, Shiga 5260829, Japan
来源：
TETRAHEDRON | 2016年 / 72卷 / 42期
基金：
日本学术振兴会;
关键词：
Atropisomer; Conformational restriction; NMR spectroscopy; Pyropheophorbide; Rotamer; Steric repulsion; SELF-AGGREGATION; PYROPHEOPHORBIDE DIMERS; ELECTRONIC-ABSORPTION; CRYSTAL-STRUCTURE; PURPLE BACTERIA; SPECTRA; RING; TRANSFORMATIONS; CONFORMATION; BARRIERS;
D O I：
10.1016/j.tet.2016.08.079
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Methyl pyropheophorbides-a possessing a (pseudo)planar substituent at the 3-position were prepared from naturally occurring chlorophyll-a. Some of the semisynthetic pi-conjugates with the chlorin skeleton took two atropisomeric conformations for the sterically demanding 3-substituents, CONMe2, NHCOMe, C[CHC(CN)(2)]=C(CN)(2), and Ph(2,3,4,5-Ph-4). Their rotational isomerization in a solution was analyzed by H-1 NMR and HPLC. Zinc complex of the 3-aryl-chlorin gave a large energy barrier for the rotation of the C3-C3(1) single bond (estimated Delta G(double dagger)--108 kJ mol(-1) at 20 degrees C) and the atropisomerically pure conformers were separated at room temperature. (C) 2016 Elsevier Ltd. All rights reserved.
引用
收藏
页码：6626 / 6633
页数：8
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