Two-step Two-intermediate Photorelease Bolm-McCulla Reaction: Dual Release of Nitrene and Atomic Oxygen Reactive Intermediates,Photochemistry and Photobiology

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Two-step Two-intermediate Photorelease Bolm-McCulla Reaction: Dual Release of Nitrene and Atomic Oxygen Reactive Intermediates
Photochemistry and Photobiology ( IF 2.6 ) Pub Date : 2021-07-09 , DOI: 10.1111/php.13485
Mahir Rashid _{1,

2} , Devora D Baker _{1,

2} , Alexander Greer _{1,

2}

Affiliation

This article is a highlight of the paper by Isor et al. in this issue of Photochemistry and Photobiology. It describes the photolysis of a dibenzothiophene sulfoximine (bearing N-phenyl imino and S-oxide groups) to produce two reactive intermediates in tandem. The sulfoximine undergoes a S–N and S–O photocleavage to release phenyl nitrene and atomic oxygen [O(³P)]. The phenyl nitrene dimerizes to azobenzene or is trapped by diethylamine to reach an azepine. From there, atomic oxygen arises in a secondary photolysis of dibenzothiophene sulfoxide. A computational analysis also reveals that the S–N bond is labile for initial nitrene release, with the secondary release of atomic oxygen by S–O cleavage. Whether future sulfoximine scaffolds can produce the reverse order release of O(³P) then nitrene, or release both simultaneously, is yet to be established. Nonetheless, molecules with dual-intermediate release, such as coupled photoaffinity labeling and cellular oxidation, are worth pursuing.

中文翻译：

两步两中间体光释放 Bolm-McCulla 反应：氮和原子氧反应中间体的双重释放

本文是 Isor 等人论文的一个亮点。在本期的光化学和光生物学中。它描述了二苯并噻吩亚砜亚胺（带有N-苯基亚氨基和S-氧化物基团）的光解作用，以串联产生两种反应性中间体。亚砜亚胺经过 S-N 和 S-O 光裂解释放苯基氮烯和原子氧 [O( ³P)]。苯基氮烯二聚成偶氮苯或被二乙胺捕获以达到氮杂。从那里，原子氧在二苯并噻吩亚砜的二次光解中产生。计算分析还表明，S-N 键对于最初的氮烯释放是不稳定的，而 S-O 裂解会二次释放原子氧。未来的亚砜亚胺支架能否产生 O( ³ P) 然后氮烯的逆序释放，或同时释放两者，尚待确定。尽管如此，具有双重中间释放的分子，如耦合光亲和标记和细胞氧化，是值得追求的。

更新日期：2021-07-09

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