Highly Efficient and Selective Syntheses of Phycobilin Derivatives toward Analysis of structure and Function of Phytochrome

藻胆蛋白衍生物的高效选择性合成用于光敏色素结构和功能的分析

• 批准号: 11440187
• 负责人: INOMATA Katsuhiko
• 金额: $ 5.44万
• 依托单位: KANAZAWA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11440187/
• 关键词: Phytochromes; Chromophore; Phycobilin Derivatives; Tetrapyrrole Compounds; Total Synthesis; Reconstitution; Structure and Function; 構造と機能; フィトクロモビリン; フィコシアノビリン; テトラピロール誘導体; テトラピロール

Phytochrome, one of the major photosensory chromo proteins in plants, mediates a variety of light responsive developmental processes in a red/far-red photo reversible manner. The chromophore named phytochromobilin (PФB) is a linear tetrapyrrole similar in structure to phycocyanobilin (PCB), which is a chromophore of the light-harvesting pigment phycocyanin and used as a substitute for PФB to reconstitute with apoproteins. In order to analyze the structural requirements of the chromophore in phytochrome, we studied on the syntheses of phycobilin derivatives and succeeded to synthesize PФB, PCB, and PCB derivatives modified at the A-, B-, C-, and D-rings in free acid forms.Total syntheses of PФB and PCB were achieved by employing our original synthetic reactions, I.e., 1) rearrangement of the tosyl group of 2-tosylpyrroles to the 5-position under acidic conditions, 2) efficient transformation of 2-bromo-5-tosylpyrroles to the corresponding 5-tosylpyrrolinones under acidic conditions, 3) … More Wittig-type coupling reaction between 5-tosylpyrrolinones and 2-formylpyrrole, 4) palladium catalyzed deprotection of allyl esters of propanoic acid side-chains.To analyze the structural requirements of the chromophore for the spectral properties of phytochrome B (PhyB), we have designed and chemically synthesized 20 analogs of PCB and reconstituted them with PhyB apoprotein (PHYB). It was found that the A-ring -acts mainly as the anchor for legation to PHYB, because the modification of the side chains at the C2 and C3 positions did not significantly influence the formation or difference spectra of adducts. In contrast, the side chains of the B- and C-rings are crucial to position the chromophore properly in the chromophore pocket of PHYB and for photo reversible spectral changes. The side-chain structure of the D-ring is required for the photo reversible spectral change of the adducts. From these studies, we concluded that each pyrrole ring of the linear tetrapyrrole chromophore plays a different role in chromophore assembly and the photo chromic properties of PhyB. Less

光敏色素是植物中主要的光敏染色体蛋白之一，以红光/远红光光可逆方式介导多种光响应发育过程。藻蓝胆素（phycocyanobilin，PCB）是捕光色素藻蓝蛋白（phycocyanin，PS）的发色团，其结构与PS B相似，是一种线性四吡咯，可替代PS B与脱辅基蛋白复合。为了分析光敏色素中发色团的结构要求，我们对藻胆素衍生物的合成进行了研究，成功地合成了游离酸形式的P-β B、PCB和在A-、B-、C-和D-环上修饰的PCB衍生物。1)2-甲苯磺酰基吡咯的甲苯磺酰基在酸性条件下重排到5-位，2）2-溴-5-甲苯磺酰基吡咯在酸性条件下有效转化为相应的5-甲苯磺酰基吡咯啉酮，3） ...更多信息 为了研究光敏色素B（Phytochrome B，PhyB）的光谱特性对生色团的结构要求，我们设计并化学合成了20个PCB类似物，并将它们与PhyB脱辅基蛋白（PhyB）重组。结果表明，A环主要起与PHYB连接的锚作用，因为C2和C3位侧链的修饰对加合物的形成和差谱没有显著影响。相反，B环和C环的侧链对于将发色团适当地定位在PHYB的发色团口袋中以及对于光可逆光谱变化是至关重要的。加合物的光可逆光谱变化需要D环的侧链结构。从这些研究中，我们得出结论，每个吡咯环的线性四吡咯发色团在发色团组装和PhyB的光致变色性能发挥不同的作用。少

项目成果

D. Sawamoto, H. Nakamura, H. Kinoshita, S. Fujinami, K. Inomata.: "Total Syntheses of Phycocyanobilin Derivatives Bearing a Modified A-Ring toward the Structure/Function Analysis of Phytochrom"Chem. Lett.. 1398-1399 (2000)

D. Sawamoto、H. Nakamura、H. Kinoshita、S. Fujinami、K. Inomata.：“带有修饰 A 环的藻蓝蛋白衍生物的全合成，用于 Phytochrom 的结构/功能分析”Chem。

Y.Ukaji: "Catalytic Asymmertric Addition of Dialkylzinc to 3,4-Dihydroisoquinoline N-Oxides Utilizing Tartaric Acid Ester as a Chiral Auxiliary"Bull.Chem.Soc.Jpn.. 73. 447-452 (2000)

Y.Ukaji：“利用酒石酸酯作为手性助剂，二烷基锌与 3,4-二氢异喹啉 N-氧化物的催化不对称加成”Bull.Chem.Soc.Jpn.. 73. 447-452 (2000)

Y. Ukaji: "Catalytic Asymmetric Addition of Dialkylzinc to 3,4-Dihydroisoquinoline N-Oxides Utilizing Tartaric Acid Ester as a Chiral Auxiliary"Bull. Chem. Soc. Jpn.. 73. 447-452 (2000)

Y. Ukaji：“利用酒石酸酯作为手性助剂，二烷基锌与 3,4-二氢异喹啉 N-氧化物的催化不对称加成”Bull。

Y. Ukaji: "Synthesis of Lythraceae Alkaloid Lasubin II via Optically Active 2-Isoxazoline"Heterocycles. 52. 563-566 (2000)

Y. Ukaji：“通过光学活性 2-异恶唑啉合成千屈菜科生物碱 Lasubin II”杂环。

H.Hanzawa, et al.: "Structural Requirement of Bilin Chromophore for the Photosensory Specificity of Phytochromes A and B"Proc. Natl. Acad. Sci. U.S.A.. 99(in press). (2002)

H.Hanzawa 等人：“Bilin 发色团对光敏色素 A 和 B 的光传感特异性的结构要求”Proc。