Abstract
Catalytic difunctionalization of alkenes has been an ideal strategy to generate structurally complex molecules with diverse substitution patterns. Although both phosphonyl and carboxyl groups are valuable functional groups, the simultaneous incorporation of them via catalytic difunctionalization of alkenes, ideally from abundant, inexpensive and easy-to-handle raw materials, has not been realized. Herein, we report the phosphonocarboxylation of alkenes with CO2 via visible-light photoredox catalysis. This strategy is sustainable, general and practical, providing facile access to important β-phosphono carboxylic acids, including structurally complex unnatural α-amino acids. Diverse alkenes, including enamides, styrenes, enolsilanes and acrylates, undergo such reactions efficiently under mild reaction conditions. Moreover, this method represents a rare example of redox-neutral difunctionalization of alkenes with H-P(O) compounds, including diaryl- and dialkyl- phosphine oxides and phosphites. Importantly, these transition-metal-free reactions also feature low catalyst loading, high regio- and chemo-selectivities, good functional group tolerance, easy scalability and potential for product derivatization.
Highlights
Catalytic difunctionalization of alkenes has been an ideal strategy to generate structurally complex molecules with diverse substitution patterns
We envisioned that the simultaneous incorporation of both phosphonyl and carboxyl groups via selective difunctionalization of enamides and other alkenes would serve as an ideal route to deliver important βphosphono carboxylic acids, including β-phosphono α-amino acids
At the beginning of this project, we challenged ourselves with realization of selective phosphonocarboxylation of enamides with CO2 via visible-light photoredox catalysis to generate valuable β-phosphono α-amino acids
Summary
Catalytic difunctionalization of alkenes has been an ideal strategy to generate structurally complex molecules with diverse substitution patterns. We report the phosphonocarboxylation of alkenes with CO2 via visible-light photoredox catalysis This strategy is sustainable, general and practical, providing facile access to important β-phosphono carboxylic acids, including structurally complex unnatural α-amino acids. Diverse alkenes, including enamides, styrenes, enolsilanes and acrylates, undergo such reactions efficiently under mild reaction conditions This method represents a rare example of redox-neutral difunctionalization of alkenes with H-P(O) compounds, including diaryl- and dialkyl- phosphine oxides and phosphites. We report the catalytic phosphonocarboxylation of diverse alkenes, including enamides, styrenes, enolsilanes, and acrylates, with CO2 (Fig. 1c) This strategy is sustainable, general, and practical, representing a rare example of redox-neutral difunctionalization of alkenes with H-P(O) compounds to generate important β-phosphono carboxylic acids with high efficiency and selectivity under mild reaction conditions
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