5437-45-6Relevant articles and documents
Fmoc-based synthesis of glycolate ester peptides for the assembly of de novo designed multimeric proteins using subtiligase
Suich, Daniel J.,Ballinger, Marcus D.,Wells, James A.,DeGrado, William F.
, p. 6653 - 6656 (1996)
An automated method utilizing Fmoc-protected amino acids has been developed for the synthesis of glycolate ester peptides as substrates for subtiligase. As a test of this methodology, peptide esters containing α-helical sequences that specify the association into 3- and 4-helix bundles were synthesized, and used to explore the suitability of subtiligase as a tool, for the generation of covalently linked bundles. The feasibility of creating de novo designed, single-chain or cyclic structures from simple, readily-synthesized modules has been demonstrated.
Engineering Dirhodium Artificial Metalloenzymes for Diazo Coupling Cascade Reactions**
Bultman, Max J.,Huang, Rui,Lewis, Jared C.,Li, Ying,Roux, Benoit,Upp, David M.
supporting information, p. 23672 - 23677 (2021/08/23)
Artificial metalloenzymes (ArMs) are commonly used to control the stereoselectivity of catalytic reactions, but controlling chemoselectivity remains challenging. In this study, we engineer a dirhodium ArM to catalyze diazo cross-coupling to form an alkene that, in a one-pot cascade reaction, is reduced to an alkane with high enantioselectivity (typically >99 % ee) by an alkene reductase. The numerous protein and small molecule components required for the cascade reaction had minimal effect on ArM catalysis. Directed evolution of the ArM led to improved yields and E/Z selectivities for a variety of substrates, which translated to cascade reaction yields. MD simulations of ArM variants were used to understand the structural role of the cofactor on ArM conformational dynamics. These results highlight the ability of ArMs to control both catalyst stereoselectivity and chemoselectivity to enable reactions in complex media that would otherwise lead to undesired side reactions.
Visible-Light-Assisted Gold-Catalyzed Fluoroarylation of Allenoates
Feng, Chao,Tang, Hai-Jun,Zhang, Xinggui,Zhang, Yu-Feng
supporting information, p. 5242 - 5247 (2020/02/28)
A strategically novel synthetic method for the fluoroarylation of allenic ester was developed that enables the expedient construction of a host of β-fluoroalkyl-containing cinnamate derivatives. The reaction proceeds through visible-light-promoted gold redox catalysis, occurs smoothly under very mild reaction conditions, accommodates a large variety of functional groups, and more importantly allows the incorporation of fluorine and aryl groups with excellent regio- and stereoselectivity. The concomitant activation mode for both the allene motif and the hydrogen fluoride is key for the success of the reaction.