Abstract
In this report, a thorough evaluation of the use of aerobically initiated, metal-free hydroacylation of various C=C and N=N acceptor molecules with a wide range of aldehydes is presented. The aerobic-activation conditions that have been developed are in sharp contrast to previous conditions for hydroacylation, which tend to use transition metals, peroxides that require thermal or photochemical degradation, or N-heterocyclic carbenes. The mildness of the conditions enables a number of reactions involving sensitive reaction partners and, perhaps most significantly, allows for α-functionalised chiral aldehydes to undergo radical-based hydroacylation with complete retention of optical purity. We also demonstrate how the resulting hydroacylation products can be transformed into other useful intermediates, such as γ-keto-sulfonamides, sultams, sultones, cyclic N-sulfonyl imines and amides.
Highlights
The development of methods to construct new chemical bonds efficiently in a selective manner whilst minimising energy usage and production of waste has, arguably, never been of greater importance.[1]
We have recently described the radical hydroacylation of vinyl sulfonates, sulfones and phosphonates, α,β-unsaturated esters and azodicarboxylates using acyl radicals generated via the aldehyde auto-oxidation pathway.[22,23,24,25,26]
We have described the use of aerobic aldehyde C–H activation for the construction of C–C and C–N bonds through the hydroacylation of vinyl sulfonates and phosphonates, α,β-unsaturated esters and azodicarboxylates
Summary
Metal-free, hydroacylation of CvC and NvN bonds via aerobic C–H activation of aldehydes, and reaction of the products thereof†. A thorough evaluation of the use of aerobically initiated, metal-free hydroacylation of various CvC and NvN acceptor molecules with a wide range of aldehydes is presented. The aerobic-activation conditions that have been developed are in sharp contrast to previous conditions for hydroacylation, which tend to use transition metals, peroxides that require thermal or photochemical degradation, or N-heterocyclic carbenes. The mildness of the conditions enables a number of reactions involving sensitive reaction partners and, perhaps most significantly, allows for α-functionalised chiral aldehydes to undergo radical-based hydroacylation with complete retention of optical purity. We demonstrate how the resulting hydroacylation products can be transformed into other useful intermediates, such as γ-keto-sulfonamides, sultams, sultones, cyclic N-sulfonyl imines and amides
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