Rh(III)-Catalyzed Synthesis of Unnatural Peptides

Ribosomal synthesis of unnatural peptides.

Combinatorial libraries of non-biological polymers and drug-like peptides could in principle be synthesized from unnatural amino acids by exploiting the broad substrate specificity of the ribosome. The ribosomal synthesis of such libraries would allow rare functional molecules to be identified using technologies developed for the in vitro selection of peptides and proteins. Here, we use a recon...

Synthesis and Conformational Studies of Unnatural Backbone Modified Peptides

Unified synthesis of mono/bis-arylated phenols via RhIII-catalyzed dehydrogenative coupling.

2,6-Bis-arylated phenols are rarely reported and are synthetically challenging. Directed C-H functionalization reactions, using a directing group (DG), might provide a convenient solution to their synthesis. However, this strategy usually results in partial cleavage of the directing group, preventing further/second C-H activation cascades. Herein we report a general strategy that allows for the...

Stereoselective terminal functionalization of small peptides for catalytic asymmetric synthesis of unnatural peptides.

The asymmetric phase-transfer catalytic alkylation of peptides has been achieved by the use of designed C(2)-symmetric chiral quaternary ammonium bromide 1 as catalyst. Excellent stereoselectivities were uniformly observed in the alkylation with a variety of alkyl halides and the efficiency of the transmission of stereochemical information was not affected by the side-chain structure of the pre...

Synthesis and Luminescence of RhIII ( phpy ) 2 ( S ∪ E ) Complexes

Complexes of the general composition Rh(phpy)2(S∪E) with phpy− = 2-(2-pyridyl)phenyl and S∪E− = diethyldithiocarbamate, 2-pyridinethiolate and 2-quinolinethiolate were prepared and characterized. The complexes with S∪E− = diethyldithiocarbamate and 2-pyridinethiolate show a low-temperature luminescence which originates from a phpy ππ∗ intraligand triplet. For the complex with S∪E− = 2-quinoline...