Visible light-mediated photolysis of organic molecules: the case study of diazo compounds

Abstract

Considering the recent rapid advancement of synthetic technologies promoted by visible light in the last 15 years, the use of photocatalysts has been rightfully justified based on the fact that...

Lighting the way to diverse cyclic architectures: expanding the horizons with photogenerated ketenes in sustainable chemistry

“…Notably, recent reports of versatile electrophilic reagents containing ketenes as molecular probes suggest their potential in the biotherapeutic field as photoaffinity probes. 73–77…”

Transition metal-catalyzed reactivity of carbenes with boronic acid derivatives for arylation (alkylation) and beyond

“…In this context, carbenes are highly reactive intermediates in organic chemistry and can undergo many transformations for the synthesis of synthetic intermediates, and these are summarized elsewhere. 3–8…”

“…Diazo compounds are versatile reagents in organic chemistry for synthesizing carbenes, and these carbenes could be generated by either thermal or photochemical decomposition of diazo compounds. 4 Similarly, metallocarbenes are generated from a suitable metal catalyst using diazocarbonyl compounds and related precursors. 5 Thus, carbenes/metallocarbenes are reactive intermediates in organic chemistry and are widely used in the synthesis of natural products and pharmaceuticals.…”

Introducing N-Sulfinylamines into Visible-Light-Induced Carbene Chemistry for the Synthesis of Diverse Amides and α-Iminoesters

“…Apart from these, modern-day chemistry has delivered ingenious methods by harnessing visible light as a crucial promoter to generate electrophilic carbene intermediates from diazo compounds. Therefore, visible light became an alternative for hazardous transition-metal catalysis due to its operationally simpler, milder, and/or greener reaction conditions . Like diazo compounds, acylsilanes are also known as an efficient carbene precursor, as they can deliver nucleophilic siloxycarbenes via 1,2-Brook rearrangement upon photolysis or by using high temperature.…”

“…The nature of the initial nucleophilic attack is the major critical point, as we never observed any cycloadduct as an intermediate or side product in our reaction conditions, even at lower temperature. On the other hand, formation of α-iminoester 9 is initiated by the excitation of α-aryldiazoacetate 8 . Excited α-aryldiazoacetate XII readily unshackles dinitrogen to form carbene intermediate XIII .…”