Late-Stage Modification of Tertiary Phosphines via Ruthenium(II)-Catalyzed C–H Alkylation

Ru(II)-catalyzed direct alkylation of tertiary phosphines via hydroarylation of activated olefins promoted by mono-N-protected amino acid (MPAA) was achieved. This protocol provides a straightforward access to a large library of Buchwald-type bulky alkylated monophosphines from commercially available biaryl phosphine. Moreover, two ruthenacycle intermediates of tertiary phosphines via C–H bond cleavage were isolated to illustrate the mechanism of P(III)-directed C–H activation.