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

页码：6626 / 6633

页数：8

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