Efficient Synthesis of Long‐wavelength Absorbing Cyanochlorophyll a Derivatives via Stereoselective Horner–Wadsworth–Emmons Reaction. (5th March 2020)

• Record Type: Journal Article
• Authors: Wu, Huiqiang; Wang, Xiangmin; Liu, Yang; Zhao, Yu; Wang, Xinyue; Lee, Woo Kyoung; Shim, Young Key; Yoon, Il; Xu, Xinming; Li, Jiazhu
• Is Part Of: Bulletin of the Korean Chemical Society. Volume 41:Number 5(2020)
• Page Start: 504
• Page End: 512
• Publication Date: 2020-03-05
• Subjects: Chlorophyll a -- Chlorin -- Cyanochlorin -- Allomerization -- Horner–Wadsworth–Emmons reaction; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/bkcs.11998
• Languages: English
• ISSNs: 0253-2964

Abstract

Abstract : In this article, we report the stereoselective Horner–Wadsworth–Emmons reaction of reactive carbonyl‐substituted chlorophyll a derivatives with diethyl cyanomethylphosphonate. We found that the formyl or keto group at the chlorin periphery can react stereoselectively with phosphonate carbanions to produce a series of cyanomethylene‐substituted chlorins with predominantly E geometry. Considering that no consistent records are available in the literature on the results of the allomerization of methyl pyropheophorbide a, we propose a reliable process for the transformation of this chlorophyll derivative. Our methodology represents a simple and efficient way for the preparation of novel, differently functionalized long‐wavelength absorbing chlorins, those can be applied for photodynamic therapy, solar cells, and other relevant purposes. Abstract : Stereoselective HWE reaction of reactive carbonyl substituted chlorophyll a derivatives with diethylcyanomethylphosphonate produced a series of cyanochlorophyll a derivatives with the long‐wavelength absorptions in the range of 677‐698 nm