Article
Chemistry, Multidisciplinary
Dong Guk Nam, Su Yong Shim, Hye-Min Jeong, Do Hyun Ryu
Summary: The highly enantioselective Darzens-type epoxidation of diazoesters with glyoxal derivatives was achieved using a chiral boron-Lewis acid catalyst and a chiral oxazaborolidinium ion catalyst, leading to the asymmetric synthesis of trisubstituted alpha,beta-epoxy esters with high yield (up to 99%) and excellent enantio- and diastereoselectivity (up to >99% ee and >20:1 dr, respectively). The synthetic potential of the method was demonstrated by the conversion of the products to various compounds such as epoxy gamma-butyrolactone, tertiary beta-hydroxy ketone, and epoxy diester.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kuldeep Singh, Idan Avigdori, Alexander Kaushansky, Natalia Fridman, Dor Toledano, Mark Gandelman
Summary: Nitrogen Lewis acids (NLAs) have emerged as a powerful tool in strong bond activation and catalysis. This article presents the synthesis and characterization of a new generation of nitrenium-based Lewis acids and demonstrates their efficiency in gram-scale hydrosilylation reactions. Experimental and theoretical studies provide insights into the mechanistic action of nitrenium Lewis acids in reduction-type reactions.
Article
Chemistry, Applied
Shuichi Nakamura, Natsuki Matsumoto, Masato Kibe, Kazuki Abe, Tsunayoshi Takehara, Takeyuki Suzuki
Summary: This study reports the enantiodivergent reaction of ketimines derived from alpha-ketoesters with malononitriles using a single chiral source, resulting in the synthesis of various optically active compounds from the obtained malononitrile-derived alpha-amino acids. A proposed reaction mechanism explains the observed enantiodivergency in high yields with high enantioselectivities.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Indranil Halder, Akshay M. Nair, Samyadev Giri, Chandra M. R. Volla
Summary: Here, we report the use of PhTeTePh as an uncommon reducing agent in the reductive hydrazo-sulfonylative difunctionalization cascade of alkynyl cyclohexadienones. Diphenyl ditelluride, a commercially available solid with good solubility in most organic solvents, was employed for the first time as a reducing agent. The protocol allowed for the synthesis of various difunctionalized dihydrochromenones and dihydrobenzofuranones in good yields under mild conditions. The reactions were scalable, and mechanistic studies were conducted. Additionally, photophysical studies revealed significant absorption (400-450 nm) and emission (520-570 nm) of the products in the visible region.
Article
Chemistry, Multidisciplinary
Jieshuai Xiao, Minyan Wang, Xuwen Yin, Shuo Yang, Pei Gu, Xueli Lv, Yue Zhao, Zhuangzhi Shi
Summary: The first asymmetric reductive (hetero)arylations of imines using aryl and heteroaryl halides enabled by a chiral cobalt-bisphosphine catalyst are reported. This approach shows good functional group compatibility and complements the reported strategy without use of organometallic reagents. Mechanistic investigations supported that aryl-cobalt, instead of an arylzinc reagent, was formed in situ in this reductive aryl-addition event.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Shuang-Long Li, Ren Wang, Jiajie Chen, Hao Zhang, Gao-Kai Hou, Xin Lu, Qing Sun, Yang Li
Summary: A Lewis acid catalyzed carbofunctionalization of styrenes with diacyl peroxides and nucleophiles has been achieved. Primary, secondary, and tertiary alkyl diacyl peroxides generated from inexpensive aliphatic acids serve as both alkylating reagents and internal oxidants for the synthesis of valuable products. This protocol offers site selectivity, broad substrate scope, and mild reaction conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Kazuki Ogura, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamuraa
Summary: A novel enantioselective vinylogous Mannich reaction was developed for the synthesis of acyclic delta-amino-alpha,beta-unsaturated carbonyl compounds, achieving excellent yields and enantioselectivities using a specific catalyst. This study provides an efficient route for the synthesis of compounds in this specific category.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Indranil Halder, Akshay M. Nair, Samyadev Giri, Chandra M. R. Volla
Summary: Here, we describe a novel reductive hydrazo-sulfonylative difunctionalization cascade of alkynyl cyclohexadienones using PhTeTePh as an uncommon reducing agent. Diphenyl ditelluride, a commercially available solid with good solubility in organic solvents, is reported for the first time as a reducing agent. The protocol enables the synthesis of diverse difunctionalized dihydrochromenones and dihydrobenzofuranones in good yields under mild conditions. Mechanistic studies were conducted to investigate the reaction mechanism, and photophysical studies of the products revealed significant absorption (400-450 nm) and emission (520-570 nm) in the visible region.
Review
Chemistry, Applied
Sahra St John-Campbell, Tom D. Sheppard
Summary: Azaenolates are the nitrogen variant of enolates, and their reactivity can be controlled by modifying the substituent on the nitrogen atom as well as the metal counterion. Various azaenolates of different metals have been found to react with a diverse set of electrophilic partners, including challenging ones. This review provides a detailed overview of the current research progress in the chemistry of imine-derived azaenolates, with a particular focus on comparing the reactivity exhibited with different metal counterions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Caifang Han, Wei Meng, Xiangqing Feng, Haifeng Du
Summary: Asymmetric intramolecular hydroalkoxylation is an important method for accessing optically active cyclic ethers. The cyclization of 2-vinylbenzyl alcohols can be catalyzed by B(C6F5)3 with low catalyst loading, resulting in high yields. A novel chiral boro-phosphate was developed to achieve high enantioselective hydroalkoxylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Songyang Jin, Xinxin Geng, Yujun Li, Ke Zheng
Summary: In this study, an environmentally-friendly light-induced Minisci alkylation of N-heteroarenes using diphenyl phosphate as catalyst under metal- and photocatalyst-free conditions was reported. The use of radical precursor redox-active esters (RAEs) as alkylating reagents for the functionalization of N-heteroarene derivatives was demonstrated, with a focus on pyridine, quinoline, and isoquinoline. Mechanistic studies indicated that diphenyl phosphate played a key role through hydrogen bonding in the catalytic cycle.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yixin Chen, Guangcheng Wu, Binbin Chen, Hang Qu, Tianyu Jiao, Yintao Li, Chenqi Ge, Chi Zhang, Lixin Liang, Xiuqiong Zeng, Xiaoyu Cao, Qi Wang, Hao Li
Summary: Self-assembly of anionic tetrahedron cage in water via metal-ligand coordination shows stability and chiral selectivity, accommodating various guest molecules in aqueous media.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yingjie Fan, Eric You, Ziwan Xu, Wenbin Lin
Summary: The study introduces a metal-organic layer (MOL), Hf-Ir-OTf, as a bifunctional photocatalyst for selective photoredox reductive coupling of ketones or aldehydes with electron-deficient alkenes. This catalyst effectively suppresses undesired dimerization and reduction of ketyl radicals, enhancing the selectivity for cross-coupling products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Gangarajulu Kesavulu, Biguvu Balachandra, Kavirayani R. Prasad
Summary: The use of lithio tris(methylthio)methane as an anion equivalent enables the synthesis of α-amino acids. Reactions with nonracemic sulfinimines yield α-sulfinamido trithioformates with excellent diastereoselectivity. Conversion of trithioformates to diverse functionalities such as α-amino acid thioesters, esters, anilides, amides, and di/tripeptides is achieved without epimerization of chiral centers.
Article
Chemistry, Multidisciplinary
Qinglin Zhang, Kang Liang, Chang Guo
Summary: A novel electrolytic system has been introduced to divert standard ionic reactivity, providing a brand-new pattern of reactivity-electricity-driven asymmetric catalysis, which serves as a privileged chiral platform for enantioselective radical allylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)