Macrolactonization of peptide thioesters catalyzed by imidazole and its application in the synthesis of kahalalide B and analogues.

  title={Macrolactonization of peptide thioesters catalyzed by imidazole and its application in the synthesis of kahalalide B and analogues.},
  author={Yangmei Li and Marc Giulionatti and Richard A. Houghten},
  journal={Organic letters},
  volume={12 10},
The macrolactonization of peptide thioester to yield cyclic depsipeptides was developed using imidazole as a catalyst. This strategy was applied to the synthesis of kahalalide B and its analogues. 

Depsipeptide synthesis using a late-stage Ag(I)-promoted macrolactonisation of peptide thioamides.

A novel macrolactonisation strategy employing a Ag(i)-promoted conversion of peptide thioamides to isoimide intermediates, which undergo site-selective intramolecular acyl transfer to serine/threonine side chains to generate the macrolactsone is reported.

Metal-free synthesis of unsymmetric bis(thioesters).

The first metal-free protocol for efficient synthesis of unsymmetric bis(thioesters) via functionalization of dithiols with two different α,β-unsaturated aldehydes is presented. The methodology

Continuous flow as a benign strategy for the synthesis of Thioesters via selective C-N bond cleavage

A metal-free C-N bond cleavage of amide functionality has been reported for the efficient and rapid synthesis of thioester in a simple flow system and includes good to excellent yields, broad functional group compatibility and can afford the thioesters in just 40 s.

The role of imidazole in peptide cyclization by transesterification: parallels to the catalytic triads of serine proteases.

This work used transition state analysis to explore the mechanism of the imidazole-catalyzed esterification of one such peptide, Ac-SAFYG-SCH2φ, and determined the acyl substitution product to be an intermediate in a competing reaction pathway involving acyl substituted of the thioester by imidrazole.

Contemporary strategies for peptide macrocyclization.

Recent solutions to some of the major challenges in this important area of contemporary synthesis of peptide macrocycles are reviewed.

Dual Roles of Methyl Ketones in Radziszewski-Type Reaction: Formal [2 + 1 + 1 + 1] Synthesis of 1,2,5-Trisubstituted Imidazoles.

A highly efficient molecular iodine mediated Radziszewski-type reaction of methyl ketones, anilines, and tosylmethyl isocyanide has been developed and is the first example wheremethyl ketones serve as the α-dicarbonyl compounds and aldehydes in Radz iszisZewski- type reactions.

Practical Synthesis of Polysubstituted Imidazoles via Iodine‐ Catalyzed Aerobic Oxidative Cyclization of Aryl Ketones and Benzylamines

A practical synthetic method for polysubstituted imidazoles via iodine-catalyzed aerobic oxidative cyclization of aryl ketones and benzylamines has been developed. It was found to tolerate a broad

Structure and Reactivity of Highly Twisted N -Acyl Imidazoles

A modular and efficient synthesis of highly twisted N-acyl imidazoles is reported. These twist amides were characterized via X-ray crystallography, NMR spectroscopy, IR spectroscopy, and DFT

Structure and Reactivity of Highly Twisted N-Acylimidazoles.

Reactivity and stability studies indicate that these twisted N-acylimidazoles may be valuable, namely as acyl transfer reagents.

Chemical peptide macrolactonization via intramolecular S‐to‐S‐to‐O acyl transfer

This work links the ribosomal synthesis of CDPs to the chemical synthesis of their active species available from campaigns of the affinity‐based selection, enabling downstream bioassays.