Article
Chemistry, Multidisciplinary
Chao Jiang, Pinhong Chen, Guosheng Liu
Summary: In this study, a novel reaction technique combining photocatalysis and copper catalysis was developed for the radical decarboxylative C(sp(3))-C(sp(3)) cross-coupling of NHPI esters and cyclopropanols, leading to the efficient synthesis of ss-benzyl ketones. The terpyridin-4'-one ligand played a vital role in the reaction by facilitating the capture of benzylic radicals by alkyl-copper species generated through the copper-catalyzed ring-opening of cyclopropanols. The reaction exhibited broad substrate scope and wide functional group compatibility, providing a new approach for C(sp3)-C(sp3) bond formation.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nikki J. Bakas, Jeffrey D. Sears, William W. Brennessel, Michael L. Neidig
Summary: This study provides critical insights into the role of TMEDA as an additive in iron-catalyzed cross-coupling reactions. By using spectroscopic and crystallographic techniques, TMEDA-iron(II)-aryl intermediates are identified in the reaction cycle and it is found that their recombination with radicals leads to highly selective product formation. This research highlights the significance of TMEDA in modulating the selectivity and catalytic performance of organoiron species in cross-coupling reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Paul J. Chirik
Summary: A cobalt-catalyzed method for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides was developed, with cobalt-ligand combinations being assessed through high-throughput experimentation. The use of cobalt(II) sources with trans-N,N'-dimethylcyclohexane-1,2-diamine (DMCyDA, L-1) resulted in optimal yield and selectivity. The transformation allowed for diverse steric and electronic properties on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile, with radical trap experiments supporting the formation of electrophile-derived radicals during catalysis.
Article
Chemistry, Multidisciplinary
Ying Qin, Lianghui Li, Jin-Yuan Liang, Kailong Li, Dongbing Zhao
Summary: This method involves the first intermolecular silacyclization strategy with Pd-catalyzed silicon-based C(sp(2))-C(sp(3) cross-coupling, allowing the assembly of structurally novel and interesting sila-benzo[b]oxepines with good functional group tolerance. The key to success lies in the stronger affinity of silicon atoms for oxygen nucleophiles than carbon nucleophiles, as well as the inherent ring-strain-release Lewis acidity of silacyclobutanes (SCBs).
Article
Chemistry, Multidisciplinary
Fu-Li Wang, Lin Liu, Chang-Jiang Yang, Cheng Luan, Jing Yang, Ji-Jun Chen, Qiang-Shuai Gu, Zhong-Liang Li, Xin-Yuan Liu
Summary: The copper-catalyzed enantioconvergent radical C(sp(3))-C(sp(2)) cross-coupling reaction of tertiary alpha-bromo-beta-lactams with organoboronate esters provides a synthetic route to valuable alpha-quaternary beta-lactams. The challenge lies in the formation of sterically congested quaternary stereocenters between tertiary alkyl radicals and chiral copper(II) species. Through the use of a copper/hemilabile N,N,N-ligand catalyst, we have succeeded in achieving this transformation and demonstrated its synthetic potential in the conversion of products into valuable building blocks. This catalytic cycle opens up new possibilities for enantioconvergent cross-coupling reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Youhao Wei, Zheng Wang, Kaifeng Wang, Jiang-Kai Qiu, Zhaoshan Wang, Haotian Li, Xiu Duan, Kai Guo, Xiaoguang Bao, Xinxin Wu
Summary: This study reports a copper-catalyzed allenic C(sp(2))-H cyanation with exceptional site-selectivity, addressing the challenge in synthetic chemistry of functionalizing allenic C(sp(2))-H bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Akash G. Tathe, Nitin T. Patil
Summary: This study reports C(sp(2))-S cross-coupling reactions of aryl iodides and arylsulfonyl hydrazides under ligand-enabled, Au(I)/Au(III) redox catalysis, highlighting the utility of this method for synthesizing various medicinally relevant biaryl sulfones without the need for prefunctionalized aryl coupling partners.
Article
Chemistry, Physical
Bryan C. Figula, Ting-An Chen, Jeffery A. Bertke, Timothy H. Warren
Summary: In this study, a radical relay C-H methylation method using a beta-diketiminate copper catalyst was developed, enabling the methylation of unactivated C(sp(3))-H bonds. By utilizing the bench-stable DABAL-Me-3 as a reagent, methylation of various substrates with both activated and unactivated C(sp(3))-H bonds was achieved with minimal overmethylation. Mechanistic studies suggested the involvement of a copper(II) methyl intermediate that reacts with methyl radicals and radicals R-center dot to form R-Me bonds.
Article
Chemistry, Multidisciplinary
Jian Luo, Bo Hu, Wenda Wu, Maowei Hu, T. Leo Liu
Summary: This study reports a redox neutral electrochemical C(sp(2))-C(sp(3)) cross-coupling reaction conducted under ambient conditions using nonprecious metal catalysts. The reaction demonstrated good yields and a broad scope, with potential applications in pharmaceuticals and natural amino acid modification. The method, which proceeds through an unconventional radical transmetalation mechanism, is highly productive and expected to have widespread applications in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Avishek Das, Nitin T. Patil
Summary: Reported in this study is a ligand-enabled gold-catalyzed C(sp2)-O cross-coupling reaction between aryl iodides and aliphatic alcohols. The usefulness of the method is demonstrated by successfully synthesizing a variety of aryl alkyl ethers, including complex biomolecules and medicinally relevant motifs. The importance of gold catalysis is highlighted by overcoming the selectivity issues commonly observed when other transition metals are used as catalysts for C-O cross-coupling reactions.
Article
Chemistry, Physical
Avishek Das, Nitin T. Patil
Summary: A ligand-enabled gold-catalyzed C(sp2)-O cross-coupling reaction between aryl iodides and aliphatic alcohols is reported. The method is demonstrated to be useful for the synthesis of various aryl alkyl ethers, including complex biomolecules and medicinally relevant motifs. The importance of gold catalysis is highlighted in overcoming selectivity issues observed with other transition metal catalysts in C-O cross -coupling reactions.
Article
Multidisciplinary Sciences
Cheng Wang, Zirui Qiao, Yulan Tian, Haijun Yang, Huaqiang Cao, Anthony K. Cheetham
Summary: Imines can be synthesized directly from phenylmethanol and ben-zylamine (or aniline) using carbon nanostructures as metal-free catalysts, yielding imines with up to 98% yield and water as the only by-product. The catalytic mechanism involves the reduction of O-2 to O-2(center dot-) by the unpaired electrons in carbon catalysts, triggering the oxidative coupling reaction to form imines, while the holes in the carbon catalysts receive electrons from the amine to restore the spin states. This work provides a new avenue for synthesizing carbon catalysts and has great potential for industrial applications.
Article
Multidisciplinary Sciences
Haigen Fu, Jingzhe Cao, Tianzhang Qiao, Yuyin Qi, Simon J. Charnock, Samuel Garfinkle, Todd K. Hyster
Summary: This study reports a highly chemoselective and enantioselective Csp(3)-Csp(3) XEC reaction catalyzed by flavin-dependent 'ene'-reductases (EREDs). The photoexcitation of the enzyme-templated charge-transfer complex enables the chemoselective reduction of alkyl halides and high enantioselectivity.
Article
Chemistry, Applied
Yan Li, He Tong, Yukun Li, Kang Chen, Yingguang Zhu
Summary: We have developed a visible light-induced transition metal-free benzylic C(sp(3))-C(sp(2)) defluorinative coupling reaction between indole derivatives and polyfluoroarenes via the sequential electron transfer-proton transfer (ET/PT) process, resulting in various polyfluorinated diarylmethanes. This protocol offers mild reaction conditions and good functional group tolerance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Xiao-Long Su, Liu Ye, Ji-Jun Chen, Xiao-Dong Liu, Sheng-Peng Jiang, Fu-Li Wang, Lin Liu, Chang-Jiang Yang, Xiao-Yong Chang, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: The development of enantioconvergent cross-coupling of racemic alkyl halides with heteroarene C(sp(2))-H bonds has been achieved using a copper(I)/cinchona-alkaloid-derived N,N,P-ligand catalytic system, leading to high enantioselectivity of alpha-chiral alkylated heteroarenes, which show promise in drug discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)