Synergistic solvent-catalyst paradigm for sustainable aerobic allylic C-H functionalization.

Natl Sci Rev

Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China.

Published: August 2025


Category Ranking

98%

Total Visits

921

Avg Visit Duration

2 minutes

Citations

20

Article Abstract

Achieving sustainable catalytic transformations requires synergistic optimization of solvent systems, catalytic motifs and energy inputs. Herein, we report a synergistic Pd/hydroquinone catalytic system that enables aerobic allylic C-H functions under ambient conditions (room temperature to 50°C, air) with high turnover frequency (TOF), using ethanol/water as a green medium. This strategy achieves unparalleled synthetic efficiency and demonstrates remarkable versatility across two pivotal transformations (alkylation and amination) involving over 90 products (up to 96% yield). It also delivers exceptional stereocontrol (up to 93% for quaternary stereocenters) and enables advanced allylic transformations within a green framework through additional synergistic catalysis. By integrating solvent engineering with cooperative catalysis, we have developed a scalable platform for the synthesis of allylic functionalized molecules with pharmaceutical interests, demonstrating how molecule-level innovation can drive sustainable industrial transformation.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC12236312PMC
http://dx.doi.org/10.1093/nsr/nwaf196DOI Listing

Publication Analysis

Top Keywords

aerobic allylic
8
allylic c-h
8
synergistic
4
synergistic solvent-catalyst
4
solvent-catalyst paradigm
4
paradigm sustainable
4
sustainable aerobic
4
allylic
4
c-h functionalization
4
functionalization achieving
4

Similar Publications

Previously published (NMe)[V(O)(μ-O)(pin)], has been shown to aerobically catalyze the oxidation of benzylic and allylic alcohols under mild conditions. Herein, we report syntheses of [V(O)(μ-O)(pin)] trimers, which are also active in OAD catalysis. Trimer formation requires an ammonium cation with at least two hydrogen atoms per cation (e.

View Article and Find Full Text PDF

The biocatalytic aerobic production of (E)-2-allylic aldehydes from their corresponding alcohols using lyophilisates of the basidiomycetous fungus Bjerkandera adusta is reported. The addition of small amounts of organic solvents to the reaction media increased the reaction and substrate conversion rates, allowing for to produce (E)-aldehydes under sustainable conditions. Citral (mixture of (E)- and (Z)-3,7-dimethylocta-2,6-dienal) was found as a result of the oxidation of geraniol ((E)-3,7-dimethyl-2,6-octadien-1-ol) as well as of nerol ((Z)-3,7-dimethyl-2,6-octadien-1-ol).

View Article and Find Full Text PDF

In this study, we describe the production of a novel high loading magnetic ionic nanoparticle network (HMINN) encompassing a functionalized imidazolium structure bridging between the core-shell magnetic nanoparticles. The network was constructed through the in situ radical polymerization of tris-vinyl imidazolium moieties on the surface of mercaptopropyl functionalized silica-coated magnetite. The structural and chemical features of the resulting material were comprehensively characterized utilizing various analytical methods such as N adsorption-desorption, FTIR, TGA, HRTEM, ICP, XPS, VSM and elemental analysis.

View Article and Find Full Text PDF

Synergistic solvent-catalyst paradigm for sustainable aerobic allylic C-H functionalization.

Natl Sci Rev

August 2025

Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China.

Achieving sustainable catalytic transformations requires synergistic optimization of solvent systems, catalytic motifs and energy inputs. Herein, we report a synergistic Pd/hydroquinone catalytic system that enables aerobic allylic C-H functions under ambient conditions (room temperature to 50°C, air) with high turnover frequency (TOF), using ethanol/water as a green medium. This strategy achieves unparalleled synthetic efficiency and demonstrates remarkable versatility across two pivotal transformations (alkylation and amination) involving over 90 products (up to 96% yield).

View Article and Find Full Text PDF

Isolation of Dehalococcoides mccartyi strain (NIT-OBY) and identification of a reductive dehalogenase dechlorinating cis-1,3-dichloropropene but not trans-1,3-dichloropropene to non-toxic propene.

J Hazard Mater

September 2025

Department of Civil and Environmental Engineering, Nagoya Institute of Technology (Nitech), Gokiso-Cho, Showa-Ku, Nagoya, Aichi 466-8555, Japan; Institute of Materials and Systems for Sustainability, Department of Civil Engineering, Graduate School of Engineering, Nagoya University, Nagoya, Aichi 46

The popular soil fumigant 1,3-dichloropropene (1,3-D) is widely used worldwide and one of the top five most-used pesticides in the United States. However, 1,3-D is classified as a Group 2B carcinogen and understanding its environmental fate is important. The aerobic degradation pathway of 1,3-D, along with the involved microorganisms and enzymes have been comprehensively described, whereas anaerobic transformation and the associated functional players remain incompletely understood.

View Article and Find Full Text PDF