Layered Chirality Relay Model in Rh(I)-Mediated Enantioselective C-Si Bond Activation: A Theoretical Study.

Org Lett

School of Chemistry and Chemical Engineering and Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 400030, P. R. China.

Published: March 2020


Category Ranking

98%

Total Visits

921

Avg Visit Duration

2 minutes

Citations

20

Article Abstract

A three-layer chirality relay model is proposed for Rh(I)-mediated enantioselective siletane activation. A chiral ligand in the back layer controls the position of the alkyne-coordinated metal center in the middle layer, which then provides a chiral environment for the incoming substrate at the front layer. A two-dimensional contour map analysis further clarified this model.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.orglett.9b04636DOI Listing

Publication Analysis

Top Keywords

chirality relay
8
relay model
8
rhi-mediated enantioselective
8
layered chirality
4
model rhi-mediated
4
enantioselective c-si
4
c-si bond
4
bond activation
4
activation theoretical
4
theoretical study
4

Similar Publications

Zinc(II) bis(triazolyl)(pyridyl)amine (Zn(BTPA)) complexes on the end of α-amino-iso-butyric acid (Aib) foldamers are able to transfer chirality from bound anions to the helical foldamer body. Zn(BTPA) could be obtained by simple synthetic methodology that allowed a range of functional groups to be installed around the binding site, exemplified with a fluorophore, a macrocyclic bridge and Aib itself. Changing functional group did not prevent chiral ligands from controlling foldamer conformation, although differences in complexation kinetics and equilibria were observed.

View Article and Find Full Text PDF

Bioorganic chemistry of natural products that control plant pathogens.

J Pestic Sci

August 2025

Department of Chemistry for Life Sciences and Agriculture, Faculty of Life Sciences, Tokyo University of Agriculture.

Developing new agrochemicals is essential for sustainable agriculture and global food security. Our group focused on natural products that control plant pathogens, conducting synthetic research across three key areas of interest: antimicrobial compounds, phytoalexins, and microbial signaling molecules. We established new methods for producing chiral allylic alcohols as useful synthetic intermediates for natural product synthesis the enantioselective synthesis of antimicrobial agents such as peniciaculins.

View Article and Find Full Text PDF

Cu/Ru Relay Catalysis Enables Functionalization of Allenic Alcohols with Stereodivergence and Skeleton Diversity.

J Am Chem Soc

September 2025

Hubei Research Center of Fundamental Science-Chemistry, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.

The stereodivergent synthesis of structurally complex molecules bearing multiple stereochemical elements represents a pivotal challenge in modern synthetic chemistry, particularly for bioactive compounds, where stereochemical nuances dictate pharmacological profiles. While stereodivergent dual catalysis has advanced full access to stereoisomers with stereogenic centers, the integration of stereodefined alkenes into chiral molecules with both stereochemical and skeletal diversification remains elusive. In this study, we report stereo- and skeleton-divergent access to chiral fluorinated -heterocycles with comprehensive stereocontrol of [(,), (,), (,), (,)] and [(,), (,), (,), (,)] enabled by a bimetallic Cu/Ru relay catalytic system, featuring redox-neutral efficiency and atom/step economy.

View Article and Find Full Text PDF

Enantioselective Synthesis of Chiral Azepines: A Cascade Strategy Featuring 1-Aza-Cope Rearrangement.

Angew Chem Int Ed Engl

August 2025

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, P.R. China.

The 1-aza-Cope rearrangement serves as a valuable method for constructing nitrogen-containing compounds; however, its asymmetric variants remain largely underexplored due to unfavorable thermodynamics and reaction reversibility. To overcome these challenges, we developed a relay catalysis system comprising tetrapeptide bis-quaternary phosphonium salts (PBPSs) in combination with a gold(I) catalyst. This strategy incorporates a ring-opening process during the rearrangement to preserve stereocenters and facilitate product formation.

View Article and Find Full Text PDF

Asymmetric Access to δ-Hydroxy α-Amino Acids Bearing Two Adjacent Stereocenters from Inert Allylic Alcohols Via Cu/Ru Relay Catalysis.

J Am Chem Soc

July 2025

Hubei Research Center of Fundamental Science-Chemistry, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.

Herein, we developed an efficient Cu/Ru relay catalytic system to achieve an asymmetric cascade reaction through merging hydrogen-borrowing and asymmetric Michael addition between inert allylic alcohols and ketoimine ester, enabling the efficient synthesis of biologically relevant chiral α-amino δ-hydroxy acid derivatives bearing two vicinal tertiary stereocenters in good yields with high diastereoselectivity and excellent enantioselectivity. This operationally simple and scalable protocol features excellent atom- and step-economy, broad substrate tolerance, and redox-neutral conditions. The synthetic utility was further exemplified through gram-scale synthesis, diverse downstream derivatizations, and a streamlined formal synthesis of l-pyrrolysine.

View Article and Find Full Text PDF