Synthesis, spectroscopic, and in vitro photosensitizing efficacy of ketobacteriochlorins derived from ring-B and ring-D reduced chlorins via pinacol-pinacolone rearrangement.
Synthesis, spectroscopic, and in vitro photosensitizing efficacy of ketobacteriochlorins derived from ring-B and ring-D reduced chlorins via pinacol-pinacolone rearrangement.
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DOI：
10.1021/jo201688c
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发表时间：
2011-11-04
影响因子：
3.6
通讯作者：
Pandey, Ravindra K.
中科院分区：
文献类型：
--
作者：
Joshi, Penny;Ethirajan, Manivannan;Goswami, Lalit N.;Srivatsan, Avinash;Missert, Joseph R.;Pandey, Ravindra K.
本文报道了一系列菌绿素的区域选择性氧化反应，这些菌绿素与氯化铁（FeCl_3）或2，3-二氯-5，6-二氰基苯醌（DDQ）反应生成相应的B环或D环还原二氢卟酚。吸电子基团的数量的影响存在于外围位置，有或没有一个稠合的isocyclic环（环E）没有作出任何显着的差异，在区域选择性氧化的吡咯环。然而，取决于取代基的性质，中间体双二羟基菌绿素在经历频哪醇-频哪酮反应条件时产生各种酮二氢卟酚。在分子中的特定位置处引入酮基可能取决于中间碳阳离子物质的稳定性。新合成的菌绿素具有很强的长波长吸收，并在体外（Colon 26细胞）产生显著的光敏化能力。在所测试的化合物中，在具有裂解的5元异环的B环的-7位上含有酮基的菌绿素显示出最好的功效。
In this report we present a regioselective oxidation of a series bacteriochlorins, which on reacting with either ferric chloride (FeCl3) or 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) yielded the corresponding ring-B or ring-D reduced chlorins. The effect of the number of electron withdrawing groups present at the peripheral position, with or without a fused isocyclic ring (ring-E) did not make any significant difference in regioselective oxidation of the pyrrole rings. However, depending on the nature of substituents, the intermediate bis-dihydroxy bacteriochlorins on subjecting to Pinacol-Pinacolone reaction conditions gave various ketochlorins. The introduction of the keto- group at a particular position in the molecule possibly depends on the stability of the intermediate carbocation species. The newly synthesized bacteriochlorins show strong long-wavelength absorption and produced significant in vitro (Colon26 cells) photosensitizing ability. Among the compounds tested, the bacteriochlorins containing a keto-group at position-7 of ring-B with cleaved 5-member isocyclic ring showed the best efficacy.
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影响因子：
3.3
作者：
KESSEL, D;SMITH, KM;HENDERSON, B
通讯作者：
HENDERSON, B
影响因子：
1.8
作者：
Kozyrev, AN;Dougherty, TJ;Pandey, RK
通讯作者：
Pandey, RK
影响因子：
7.3
作者：
Gryshuk, AL;Chen, YH;Pandey, RK
通讯作者：
Pandey, RK
影响因子：
1.8
作者：
Kozyrev, AN;Zheng, G;Pandey, RK
通讯作者：
Pandey, RK
影响因子：
1.8
作者：
Minehan, TG;Kishi, Y
通讯作者：
Kishi, Y