Abstract:
In our pursuit of tailored compounds, we explore two research frontiers. First, we introduce a streamlined method to craft σ2λ3-1,3-azaphospholes from common alkynes. A [3+2]-cycloaddition with imidazoliumyl-substituted triflato-phosphanes yields azaphospholium salts, readily reducible to azaphospholes. This versatile process achieves impressive yields, offering access to diverse examples with yields up to 99%. We delve into mechanistic insights, unveiling the chemical choreography.
Shifting focus, we present innovative P1 building blocks embodied by cationic imidazoliumyl-phosphinidene [LC−P]+. Overcoming the scarcity of isolable phosphinidenes, we design a phosphinidene with a strategic leaving group. Its transfer initiates various transformations, including thioketone conversion to cationic phosphaalkenes. Nucleophiles are capable of replacing the imidazoliumyl moiety, granting access to known and unprecedented phosphaalkenes. We explore the synthesis scope and mechanistic nuances.