Outer-Sphere Control for Divergent Multicatalysis with Common Catalytic Moieties

We herein report two examples of
one-pot, simultaneous reactions,
mediated by multiple, orthogonal catalysts with the same catalytic
motif. First, BINOL-derived chiral phosphoric acids (CPA) and phosphothreonine
(pThr)-embedded peptides were found to be matched for two different
steps in double reductions of bisquinolines. Next, two π-methylhistidine
(Pmh)-containing peptides catalyzed enantio- and chemoselective acylations
and phosphorylations of multiple substrates in one pot. The selectivity
exhibited by common reactive moieties is adjusted solely by the appended
chiral scaffold through outer-sphere interactions.