Editorial Material
Chemistry, Multidisciplinary
Nathan W. Dow
Summary: Nathan Dow is a third-year graduate student at Princeton University working in the lab of Prof. David MacMillan. His research focuses on combining photoredox activation with copper catalysis to achieve challenging chemical transformations through open-shell mechanisms.
Article
Chemistry, Multidisciplinary
Chaorui Ma, Jingyu Shen, Chaofan Qu, Tianju Shao, Shanshan Cao, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: Chemodivergent synthesis is achieved in asymmetric photocatalysis using a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer. Different inorganic bases enable the formation of valuable products from the three-component radical tandem transformations. The distinct pKa environment plays a key role in the success of this process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chaorui Ma, Jingyu Shen, Chaofan Qu, Tianju Shao, Shanshan Cao, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: Chemodivergent synthesis was achieved using asymmetric photocatalysis. By using a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer, different inorganic bases were used to enable the formation of two sets of valuable products from a three-component radical tandem transformation. The key to success was the distinct pK(a) environment, which determined the fate of the radicals formed on the quinoxalin-2(1H)-one rings.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Itaru Nakamura, Mai Tachibana, Riku Konta, Hiroki Tashiro, Masahiro Terada
Summary: Cu-catalyzed reactions of N-alkoxy-2-methylanilines and alcohols in the presence of IPrCuBr and AgSbF6 afford meta-aminophenol derivatives through a [1,3]-rearrangement and an oxa-Michael reaction.
Article
Chemistry, Physical
Lei Xu, Sishi Zhong, Qian Yang, Jie Wei, Jiaming Zou, Hongxiang Li, Yunfei Cai
Summary: This study developed a new asymmetric radical-mediated Piancatelli-type rearrangement reaction, which allows for a three-component reaction of diverse carbon-centered radical precursors and anilines with high yields, enantioselectivities, and diastereoselectivities. The synthesized products can be applied for late-stage functionalization of valuable drug targets or natural products. The diastereoselectivity of the rearrangement reaction is controlled by Dy(III)-accelerated Z/E isomerization of Piancatelli intermediates, and the chiral Bronsted acid-catalyzed 4π-electrocyclization of pentadienyl carbocation intermediates is a key step determining both reaction rate and enantioselectivity.
Article
Chemistry, Organic
Xiao-Qian Zhang, Congdi Zhang, Zhiyou Hu, Youliang Wang
Summary: The gold-catalyzed divergent additions of trans-2-butene-1,4-amino alcohols' N-H and O-H groups to alkynes, followed by a cascade (Aza-) Claisen rearrangement/cyclization sequence, has been reported. This reaction produces functionalized dihydropyrrole and dihydrofuran products.
Article
Chemistry, Organic
Shi-Yun An, Jin-Long Zhang, Gao-Xi Jiang
Summary: A novel one-step synthesis of tetraphenyl substituted furoindoles was reported, involving acid-catalyzed cascade approach of commercially available m-aminophenols with readily accessible alpha-hydroxyaldehydes. The tandem-reactions included nucleophilic addition, aldimine condensation, pinacol rearrangement, alpha-iminol rearrangement, cyclization and dehydration aromatization process, with a yield of furoindoles up to 75%.
Article
Chemistry, Physical
Michael J. Tilby, Damien F. Dewez, Loic R. E. Pantaine, Adrian Hall, Carolina Martinez-Lamenca, Michael C. Willis
Summary: This study presents a late-stage functionalization strategy to convert sulfonamides into pivotal sulfonyl radical intermediates. The methodology utilizes a metal-free photocatalytic approach to access radical chemistry, enabling the combination of pharmaceutically relevant sulfonamides with an assortment of alkene fragments. The sulfinate anion can also be readily obtained, expanding the options for sulfonamide functionalization. Mechanistic studies indicate the involvement of energy-transfer catalysis (EnT).
Article
Chemistry, Applied
Denisa Hidasova, Radek Pohl, Ivana Cisarova, Ullrich Jahn
Summary: The study presents an asymmetric synthesis method for N,2,3,4,5-pentasubstituted pyrrolidines through oxidative single-electron transfer-catalyzed tandem reactions, enabling the diastereodivergent single-step synthesis of pyrrolidines with four contiguous stereogenic centers by setting the configuration of two stereocenters and generating two more in a selective manner. The stereoselectivity is rationalized by a predictive model.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Xiangzhang Tao, Shengyang Ni, Lingyu Kong, Yi Wang, Yi Pan
Summary: A photocatalyzed 1,3-boron shift of allylboronic esters involving consecutive 1,2-boron migrations and Smiles-type rearrangement has been reported, leading to the formation of various terminally functionalized alkyl boronates. The reactions can tolerate different types of migrating variations of heteronuclei radicals and dearomatization processes, allowing for the elaboration of highly functionalized boron-containing frameworks.
Article
Chemistry, Multidisciplinary
Junki Matsumoto, Yusei Nakashima, Takashi Nishikata
Summary: Here, an efficient method using transition metal catalysts to control the reaction of alpha-bromocarbonyls with a styrene moiety is reported. The iron catalyst leads to the formation of cyclic compounds with a C-C double bond, while the copper catalyst produces halogenated cyclic compounds.
Article
Chemistry, Organic
Gwilherm Evano, Cedric Theunissen
Summary: Copper is an efficient and attractive metal for catalysis. Copper complexes are utilized to catalyze various reactions, including those involving radicals, due to their availability, low cost, and limited toxicity. This account summarizes our contributions to the catalysis of radical reactions from organic halides with copper complexes.
Article
Chemistry, Organic
Ling Li, Shiqi Zhang, Xiongfei Deng, Guangxun Li, Zhuo Tang, Gang Zhao
Summary: A metal-free and operationally simple strategy has been developed for the synthesis of α-imino ketones with high regioselectivity, as well as various N,O-ketals with high regioselectivities and diastereoselectivities through cascade reactions in one pot.
Article
Chemistry, Multidisciplinary
Stephan P. Blum, Tarik Karakaya, Dieter Schollmeyer, Artis Klapars, Siegfried R. Waldvogel
Summary: This study presents a novel dehydrogenative electrochemical sulfonamide synthesis protocol for non-prefunctionalized aromatic compounds, utilizing the amidosulfinate intermediate and a highly convergent reaction with SO2 and amines. The strategy involves direct anodic oxidation and nucleophilic attack, leading to high efficiency in introducing the sulfonamide group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Huan Zhou, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed asymmetric C-(sp(3))-C cross-coupling is an efficient method for the rapid synthesis of enantioenriched molecules. Chiral copper catalysts have been designed to promote a variety of asymmetric radical C(sp(3))-C cross-coupling reactions with high efficiency and enantioselectivity. The key to success lies in the design of chiral ligands to initiate the reaction and achieve enantiocontrol over the highly reactive prochiral alkyl radical species.
