Visible-Light-Initiated Multicomponent Reactions of α-Diazoesters to Access Organophosphorus Compounds

Abstract

A simple visible-light-initiated strategy has been established for the construction of organophosphorus compounds via aerobic multicomponent reaction of α-diazoesters, cyclic ethers, and P­(O)H compounds under air. A number of phosphonates and phosphinates could be efficiently isolated in moderate to good yields without the use of photosensitizers and metal reagents. This multicomponent reaction has advantages of mild condition, simple operation, eco-friendly energy, good functional-group tolerance, and gram-scale synthesis.

Visible‐Light‐Promoted Tandem Oxyphosphorylation Etherification of α‐Diazoesters to Access Phosphoric Esters

“…Combined with our ongoing research interest in the development of P‐centered radical reactions [11] and others, [12] herein, we wish to report an efficient and novel strategy for the synthesis of phosphoric esters via visible‐light‐promoted tandem oxyphosphorylation etherification reactions of α diazoesters with P(O)H and THF (reagent and solvent) under mild conditions in the absence of any catalysts and additives (Scheme 1, d). It is worth to mention that a similar work is reported by Wei′s group when we are preparing the manuscript [13] …”

“…On the basis of the above mechanistic experiments and relevant literature reports, [9][10]13] a plausible reaction mechanism for this visible-light-promoted tandem oxyphosphorylation etherification reaction of α diazoesters to access phosphoric esters was proposed in Scheme 3. Initially, the 2-diazo-2phenylacetate 1 a was activated to generate the free carbene intermediate A via denitrogenation under visible-light-irradiated, which could be trapped by the THF to produce the oxonium ylide intermediate B. on the other hand, the radical intermediates C and D would be generated through a proton transfer process between free carbene intermediate A and 2 a.…”

“…The supporting information includes the general information about materials and instruments used in experiments, light source in detail, scale-up reaction, preliminary mechanistic studies, analytical data( 1 H, 13 C, 31 P, 19 F NMR spectra, HRMS) and copies of spectra.…”

“…It is worth to mention that a similar work is reported by Wei's group when we are preparing the manuscript. [13]…”

Visible light-induced carbene reactivity of acceptor diazoalkanes: deconstructive difunctionalizations of cyclic ethers with nucleophiles

“…2 In 2018, a green synthetic strategy for free carbene was discovered by Davies and Jurberg via visible light-induced photolysis of aryl diazoacetates. 3 Afterwards, the groups of Zhou, 4 Koenigs, 5 Xuan, 6 Wei, 7 Sen 8 and Jiang 9 further developed a series of elegant visible light-induced carbene-transfer reactions of aryl diazoacetates. Notably, these aryl/acceptor carbenes could be trapped by cyclic ethers to generate oxonium ylide intermediates.…”