Modulation of Carbene Spin State Population through Precursor Photophysics

Jenks, William S.; Heying, Melanie J.; Rockafellow, Erin M.

doi:10.1021/ol802934w

Cited by 12 publications

(9 citation statements)

References 20 publications

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“…The system is novel in that the compound incorporates photocleavable S-N and S-O bonds for a tandem process. Other work has been published on nitrenes, carbenes and atomic O from photolysis of sulfilimines, sulfoxides, pyridine N-oxide and related compounds (13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25), but by nature are one-step processes. Relatedly, simultaneous formation of reactive intermediates has also been reported.…”

Section: Commentarymentioning

confidence: 99%

Two‐step Two‐intermediate Photorelease Bolm‐McCulla Reaction: Dual Release of Nitrene and Atomic Oxygen Reactive Intermediates

Rashid

Baker

Greer

2021

Photochem & Photobiology

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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 Nphenyl 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( 3 P)]. 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( 3 P) 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.

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Section: Commentarymentioning

confidence: 99%

Two‐step Two‐intermediate Photorelease Bolm‐McCulla Reaction: Dual Release of Nitrene and Atomic Oxygen Reactive Intermediates

Rashid

Baker

Greer

2021

Photochem & Photobiology

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“…In 2007, Jenks et al developed C,S-sulfonium ylides based on the thiophene moiety as a useful precursor for carbenes using a photochemical activation methodology (Scheme 1a) [9]. The synthesized sulfonium ylides were stable, easy to handle, and could generate free carbenes using ultraviolet (UV) irradiation without a catalyst [10,15,17]. These studies reported that onium ylides with relatively large conjugated systems could photochemically generate the corresponding carbene species.…”

Section: Introductionmentioning

confidence: 99%

Selenonium ylides: synthesis, characterization, and applications to photo-induced cyclopropanation reactions

Yamaguchi

Inagawa

Itoh

2022

Photochem Photobiol Sci

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Carbenes are important and highly reactive intermediates for the synthesis of various complex molecules. They are now an indispensable chemical species in organic chemistry and are used frequently to synthesize complex compounds in drug discovery chemistry. In general, carbenes are synthesized by a combination of transition metal catalysts and diazo compounds or by the decomposition reactions of diazo compounds. This paper reports the development of the visible light for the photochemical generation of carbenes from a novel C,Se-selenonium ylide. Overall, this photochemical carbene generation method using C,Se-selenonium ylide does not require a catalyst, is simple to perform, and enables highly efficient cyclopropanation reactions with alkenes.

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“…51 Indeed, a triplet state carbene intermediate yields a malonate whereas a singlet-state carbene undergoes an O-H insertion producing 2-methoxy malonate. The spin-state selectivity is also supported by the stereochemical outcome of the addition of the intermediate carbene to cis-4-octene.…”

mentioning

confidence: 99%