Synthesis of tailored hydrodipyrrins and their examination in directed routes to bacteriochlorins and tetradehydrocorrins
Synthesis of tailored hydrodipyrrins and their examination in directed routes to bacteriochlorins and tetradehydrocorrins
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定制的氢二吡林的合成及其在菌绿素和四氢可林的定向途径中的检测
DOI：
10.1039/c7nj01892d
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发表时间：
2017
影响因子：
3.3
通讯作者：
J. Lindsey
中科院分区：
文献类型：
--
作者：
Shaofei Zhang;M. N. Reddy;O. Mass;Han;Gongfang Hu;J. Lindsey
还原的四吡咯的化学比完全不饱和（卟啉）类似物的化学发展得更少，但鉴于氢卟啉的天然作用（例如，叶绿素、细菌叶绿素）和收缩的氢卟啉（钴胺素）。1-（二甲氧基甲基）-2，3-二氢-3，3-二甲基二吡咯（称为二氢二吡咯-缩醛）的自缩合得到相应的菌绿素或四脱氢可啉，其结果可通过选择催化条件来控制。在合成大环化合物的周边安装不同图案的取代基的能力对于仿生研究是必不可少的。这里，18个新目标（和9种中间体）氢二吡咯，其涵盖一系列二吡咯饱和水平（二氢，四氢，六氢）和配备不同的α-吡咯（-H、-SMe、-SPh、-Br、-Me、-CO2 R、二氧硼杂环戊烷基）和α-吡咯啉（甲基、甲酰基、二甲氧基甲基、氧代、甲氧基、甲硫基、亚氨基甲基、乙氧基羰基乙烯基，二氰基乙烯基）取代基，并在菌绿素的直接合成中进行了研究。这些路线-受二氢卟酚直接路线的启发-依赖于两个氢二吡咯的缩合以产生氢胆素，然后闭环形成大环。以非常低的产率获得了四种新的不对称取代的菌绿素;作为分支，发现了三种新的四氢可啉（镍螯合物）的有效途径，包括两种B，D-四氢可啉（吡咯啉-吡咯A-D环连接）和一种B，C-四氢可啉（吡咯啉-吡咯啉A-D环连接）。总之，这项研究加深了我们对氢二吡咯和氢胆素作为氢卟啉前体的化学性质的理解。
The chemistry of reduced tetrapyrroles is less developed than that of the fully unsaturated (porphyrin) analogues, yet is of comparable importance given the natural roles of hydroporphyrins (e.g., chlorophylls, bacteriochlorophylls) and contracted hydroporphyrins (cobalamin). The self-condensation of a 1-(dimethoxymethyl)-2,3-dihydro-3,3-dimethyldipyrrin (termed a dihydrodipyrrin-acetal) affords the corresponding bacteriochlorin or tetradehydrocorrin with the outcome potentially controllable by choice of the catalysis conditions. The ability to install distinct patterns of substituents about the perimeter of the synthetic macrocycles is essential for biomimetic studies. Here, 18 new target (and 9 intermediate) hydrodipyrrins encompassing a range of dipyrrin saturation levels (dihydro, tetrahydro, hexahydro) and equipped with diverse α-pyrrole (-H, -SMe, -SPh, -Br, -Me, -CO2R, dioxaborolanyl) and α-pyrroline (methyl, formyl, dimethoxymethyl, oxo, methoxy, methylthio, iminomethyl, ethoxycarbonylvinyl, dicyanovinyl) substituents have been prepared and examined in the directed synthesis of bacteriochlorins. The routes – inspired by a directed route to chlorins – rely on condensation of two hydrodipyrrins to produce a hydrobilin followed by ring closure to form the macrocycle. Four new unsymmetrically substituted bacteriochlorins were obtained in very low yields; as an offshoot, efficient routes to three new tetradehydrocorrins (nickel chelates) were discovered, including two B,D-tetradehydrocorrins (pyrroline–pyrrole A–D ring junction) and one B,C-tetradehydrocorrin (pyrroline–pyrroline A–D ring junction). Taken together, this study deepens our understanding of the chemistry of hydrodipyrrins and hydrobilins as precursors to hydroporphyrins.
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在 3 位和 13 位带有助色团的合成二氢卟酚。
DOI：
10.1021/jo060208o
发表时间：
2006
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Laha,JoydevK;Muthiah,Chinnasamy;Taniguchi,Masahiko;McDowell,BrianE;Ptaszek,Marcin;Lindsey,JonathanS
通讯作者：
Lindsey,JonathanS
影响因子：
3.6
作者：
Kim, HJ;Lindsey, JS
通讯作者：
Lindsey, JS
2,3,4,5-四氢-1,3,3-三甲基二吡林（一种看似简单的氢卟啉前体）的精制合成。
影响因子：
3.4
作者：
Ptaszek,Marcin;Bhaumik,Jayeeta;Kim,Han-Je;Taniguchi,Masahiko;Lindsey,JonathanS
通讯作者：
Lindsey,JonathanS
影响因子：
62.1
作者：
Lindsey, Jonathan S.
通讯作者：
Lindsey, Jonathan S.
通过四氢胆烯-a 中间体合成内消旋二氢卟酚。
DOI：
10.1021/jo0104835
发表时间：
2001
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Taniguchi,M;Ra,D;Mo,G;Balasubramanian,T;Lindsey,JS
通讯作者：
Lindsey,JS