Taniguchi Masahiko, Kim Man Nyoung, Ra Doyoung, Lindsey Jonathan S
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, USA.
J Org Chem. 2005 Jan 7;70(1):275-85. doi: 10.1021/jo048440m.
Chlorins/oxochlorins bearing distinct patterns of substituents are valuable compounds in bioorganic and materials chemistry. Treatment of a 5,10-diaryl-substituted chlorin or oxochlorin with TFA-d(1) resulted in selective deuteriation of the remaining meso positions (15, 20) rather than any of the beta-pyrrolic positions. Electrophilic iodination or bromination of a 5,10-diaryl-substituted chlorin proceeded with high regioselectivity, affording the 5,10-diaryl-15-halo-substituted chlorin. Iodination or bromination of a free base 5,10-diaryloxochlorin gave a mixture of products arising through halogenation at the 15-, 20-, and beta-pyrrolic positions, while bromination of a zinc 5,10-diaryloxochlorin selectively gave the 5,10-diaryl-20-bromo-substituted oxochlorin. The Suzuki coupling reaction of a phenyl boronic acid derivative and a 5,10-diaryl-15-iodooxochlorin or 5,10-diaryl-20-bromooxochlorin gave the corresponding 5,10,15- or 5,10,20-triaryloxochlorin. The introduction of a third aryl substituent into the chlorin or oxochlorin causes an approximately 5-nm red shift of the long wavelength Q(y) absorption band. Two phenylethyne-linked oxochlorin-oxochlorin dyads in distinct metalation states (zinc/free base, free base/zinc) were prepared by Sonogashira coupling reactions of a 5,10-diaryl-20-bromooxochlorin and a 10-substituted ethynylphenyl oxochlorin. This study provides access to new chlorins/oxochlorins that can be utilized in diverse applications.
带有不同取代基模式的二氢卟吩/氧化二氢卟吩是生物有机化学和材料化学中有价值的化合物。用TFA-d(1)处理5,10-二芳基取代的二氢卟吩或氧化二氢卟吩会导致其余中位（15、20）发生选择性氘代，而不是任何β-吡咯位置。5,10-二芳基取代的二氢卟吩的亲电碘化或溴化反应具有高区域选择性，得到5,10-二芳基-15-卤代二氢卟吩。游离碱5,10-二芳基氧化二氢卟吩的碘化或溴化反应得到在15-、20-和β-吡咯位置卤化产生的产物混合物，而锌5,10-二芳基氧化二氢卟吩的溴化反应选择性地得到5,10-二芳基-20-溴代氧化二氢卟吩。苯基硼酸衍生物与5,10-二芳基-15-碘代氧化二氢卟吩或5,10-二芳基-20-溴代氧化二氢卟吩的铃木偶联反应得到相应的5,10,15-或5,10,20-三芳基氧化二氢卟吩。在二氢卟吩或氧化二氢卟吩中引入第三个芳基取代基会使长波长Q(y)吸收带发生约5 nm的红移。通过5,10-二芳基-20-溴代氧化二氢卟吩与10-取代乙炔基苯基氧化二氢卟吩的Sonogashira偶联反应制备了处于不同金属化状态（锌/游离碱、游离碱/锌）的两个苯乙炔连接的氧化二氢卟吩-氧化二氢卟吩二元体。本研究提供了获得可用于多种应用的新型二氢卟吩/氧化二氢卟吩的途径。
