Article
Chemistry, Multidisciplinary
Yang Zhou, Hang Chen, Panpan Lei, Chunming Gui, Haifeng Wang, Qiongjiao Yan, Wei Wang, Fener Chen
Summary: This article describes a method for palladium-catalyzed allylic substitution using readily available amino acids under mild conditions. The chemoselectivity and multiple allylation can be controlled by adjusting the reaction conditions. This convenient approach allows for the synthesis of valuable N,O-diallylated amino acids with high yields and good functional group tolerance.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Anselme Geulin, Yann Bourne-Branchu, Kawther Ben Ayed, Thomas Lecourt, Antoine Joosten
Summary: 3-Amino-3-deoxyglycosides are important nitrogen-containing sugars, with many important ones having a 1,2-trans configuration. The synthesis of 3-amino-3-deoxyglycosyl donors that can form a 1,2-trans glycosidic linkage is a significant challenge due to their biological applications. This work presents a new sequence involving Ferrier rearrangement and subsequent aza-Wacker cyclization for the rapid synthesis of orthogonally protected 3-amino-3-deoxyglycals. Additionally, the epoxidation/glycosylation of a 3-amino-3-deoxygalactal derivative was successfully achieved with high yield and diastereoselectivity, demonstrating FAWEG as a new approach for accessing 1,2-trans 3-amino-3-deoxyglycosides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Bryant Pero, Mark W. Peczuh
Summary: A new synthesis of carbohydrate-based oxepines using 2,3;4,6-di-O-acetonide mannose as a key starting material is reported. The oxepine is an important precursor used in the synthesis of septanose glycomimetics of mannopyranosides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Juyeol Lee, Young Ho Rhee
Summary: This study presents a palladium-catalyzed polar inversion reaction where glycals and their isomers can act as nucleophiles. The reaction exhibits high regio- and stereoselectivity in the presence of various aromatic and aliphatic aldehydes, demonstrating its synthetic utility in the concise synthesis of the tetrahydropyran fragment of the anticancer natural product mucocin.
Article
Chemistry, Organic
Wang Jingrui, Feng Yongkui, Wang Nengzhong, Huang Nianyu, Yao Hui
Summary: C-Glycosides have attracted attention in the fields of medicine and biology due to their physiological activities and stability. This paper reports a method for preparing high stereoselectivity beta-C-glycosides through a specific reaction at room temperature, providing a reliable method for the rapid construction of C-glycoside libraries.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yaxin Zeng, Hui Yang, Jiayi Du, Qin Huang, Guoliang Huang, Ying Xia
Summary: The control of linear/branched selectivity in transition-metal catalyzed allyl-allyl cross-coupling reactions has been investigated in this study. It has been found that the terminal/internal regioselectivity can be switched by fine-tuning the rhodium catalytic system. Different types of 1,5-dienes are produced with good yields, exhibiting isomerized terminal, internal, and terminal regioselectivity.
Article
Chemistry, Organic
Mei Yang, He Zhang, Yuanhong Liu
Summary: A nickel-catalyzed direct reaction between allylic alcohols and benzyl nitrile derivatives has been developed. The method exhibits high regioselectivity, wide substrate scope, and functional group compatibility, resulting in good to excellent yields of nitriles bearing an alpha-tertiary or quaternary carbon center. BSA is identified as the effective additive for facilitating the coupling process mainly for alkyl allylic alcohols.
Review
Chemistry, Multidisciplinary
Subhabrata Dutta, Trisha Bhattacharya, Daniel B. Werz, Debabrata Maiti
Summary: Allylation reactions, pioneered by Tsuji and Trost, are essential C-C bond-forming transformations with broad applications in synthetic chemistry, bioactive compounds, and pharmaceutical industries. The development of synthetic strategies and the emergence of site-selective C-H activation have further expanded the scope of allylation reactions, eliminating the need for pre-functionalized substrates and activated allylating reagents.
Article
Chemistry, Multidisciplinary
Sijing Xue, Alexander Lucht, Jordi Benet-Buchholz, Arjan W. Kleij
Summary: The challenging metal-catalyzed asymmetric synthesis of highly functional quaternary carbon centers using decarboxylative C(sp(3))-C(sp(3)) bond formation reactions has been successfully reported in this study. By activating a key substrate, a vinyl cyclic carbonate, both the requisite nucleophile and electrophile reaction partner were provided for the asymmetric cross-coupling process. Through extensive screening of reaction conditions, additives and catalyst precursors, a protocol was developed that allowed access to a series of compounds featuring densely functionalized, elusive quaternary carbon stereocenters in appreciable yield and with enantiomeric ratios (er's) of up to 90 : 10.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Xiangbin Bai, Linlin Qian, Hong-Hao Zhang, Shouyun Yu
Summary: This study presents an enantioselective radical alkylation of 4-alkyl-1,4-dihydropyridines with Morita-Baylis-Hillman (MBH) adducts using dual photoredox/palladium catalysis, yielding products with good yields and enantioselectivity. The use of Ding's spiroketal-based bis-(phosphine) (SKP) ligand is crucial for achieving satisfactory regio- and enantioselectivity in this reaction. The resulting alpha,beta-unsaturated ester can be easily reduced to a synthetically useful chiral allyl alcohol.
Article
Chemistry, Multidisciplinary
Narayanaswamy Jayaraman
Summary: Unsaturated monosaccharides expand the reactivity scope in sugars, leading to new methodologies, molecular structures, and functional entities. Endocyclic or exocyclic unsaturation as reactive moieties can lead to largely unknown structures through one carbon homologations. Molecular shifts and rearrangements allow interchanging reactivities from one carbon to another in unsaturated sugars, with activations of exocyclic unsaturated sugars offering newer possibilities to sugar chemistry reactions. Personal reflections stem from decades of explorations in unsaturated sugars from varied perspectives.
Article
Chemistry, Organic
Perali Ramu Sridhar, Intzar Ali, M. V. Kamala Lakshmi
Summary: This study reveals an expeditious method for synthesizing monosaccharides and disaccharides with 3-oxo-glycal units. Several monosaccharides and disaccharide-derived glycals are converted to the corresponding hexenuloses through three steps involving halo-alkoxylate ion, dehydrohalogenation, and ketalyzation reactions. The importance and generality of the methodology are demonstrated by the synthesis of various 3-oxo-glycals. Additionally, the protocol is successfully applied to synthesize a rare-sugar disaccharide donor unit found in the reported natural product versipelostatin.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sijing Xue, Bart Limburg, Debasish Ghorai, Jordi Benet-Buchholz, Arjan W. Kleij
Summary: Dual palladium/photoredox-catalysis is an effective method for the decarboxylative asymmetric synthesis of vicinal alpha,beta-tri/tetra- or alpha,beta-tetrasubstituted homoallylic alcohols using Hantzsch-type esters as radical precursors. This methodology utilizes vinyl cyclic carbonates as accessible reagents to provide the target molecules in appreciable to good yields, high branch selectivity, and enantiomeric ratios of up to 94:6, making it a rare example of using prochiral electrophiles for the creation of vicinal congested carbon centers.
Article
Chemistry, Physical
Simon Sieger, Ilja Lubins, Bernhard Breit
Summary: A highly versatile palladium-catalyzed allylation reaction has been reported, providing a waste-free access to allylated nucleophiles with unlimited possibilities for further functionalization. The reaction can be conducted using propadiene in toluene, and the mechanism is supported by deuterium labeling experiments.
Article
Chemistry, Physical
Simon V. Sieger, Ilja Lubins, Bernhard Breit
Summary: A highly versatile palladium-catalyzed allylation reaction using various pronucleophiles has been reported. Through the use of propadiene in toluene, this reaction provides an efficient and waste-free method to obtain allylated nucleophiles with unlimited potential for further functionalization. The Pd/BINAP system is not only capable of adding N-, O-, and S-pronucleophiles, but also C-pronucleophiles to allene. The plausible mechanism is supported by deuterium labeling experiments.
Article
Chemistry, Organic
Lin-Lin Zhang, Bing-Chao Da, Shao-Hua Xiang, Shuai Zhu, Zi-Yun Yuan, Zhen Guo, Bin Tan
Article
Multidisciplinary Sciences
Lei Zhang, Shao-Hua Xiang, Jun (Joelle) Wang, Jian Xiao, Jun-Qi Wang, Bin Tan
NATURE COMMUNICATIONS
(2019)
Article
Chemistry, Multidisciplinary
Yong-Bin Wang, Quan-Hao Wu, Zhi-Peng Zhou, Shao-Hua Xiang, Yuan Cui, Peiyuan Yu, Bin Tan
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Organic
Dong-Liang Lu, Ye-Hui Chen, Shao-Hua Xiang, Peiyuan Yu, Bin Tan, Shaoyu Li
Correction
Multidisciplinary Sciences
Lei Zhang, Shao-Hua Xiang, Jun (Joelle) Wang, Jian Xiao, Jun-Qi Wang, Bin Tan
NATURE COMMUNICATIONS
(2019)
Article
Multidisciplinary Sciences
Shuai Zhu, Ye-Hui Chen, Yong-Bin Wang, Peiyuan Yu, Shao-Yu Li, Shao-Hua Xiang, Jun-Qi Wang, Jian Xiao, Bin Tan
NATURE COMMUNICATIONS
(2019)
Article
Chemistry, Multidisciplinary
Shengyi Yan, Wang Xia, Shaoyu Li, Qiuling Song, Shao-Hua Xiang, Bin Tan
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Correction
Chemistry, Multidisciplinary
Shengyi Yan, Wang Xia, Shaoyu Li, Qiuling Song, Shao-Hua Xiang, Bin Tan
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Review
Chemistry, Multidisciplinary
Jun Kee Cheng, Shao-Hua Xiang, Shaoyu Li, Liu Ye, Bin Tan
Summary: Atropisomerism is a stereochemical behavior exhibited by three-dimensional molecules with rotationally restricted sigma bonds, and compounds with atropisomerically chiral properties are increasingly utilized in fields where molecular asymmetry is influential. There is a steady demand for atroposelective synthesis, leading to conceptually novel and streamlined methods for expanding the structural diversity of atropisomers. This review summarizes key achievements in the stereoselective preparation of biaryl, heterobiaryl, and nonbiaryl atropisomers between 2015 and 2020, emphasizing synthetic strategies for each structural class and potential applications of atropochiral targets.
Article
Chemistry, Multidisciplinary
Jian Zhang, Jun Wei, Wei-Yi Ding, Shaoyu Li, Shao-Hua Xiang, Bin Tan
Summary: Pnictogen-bonding catalysis based on sigma-hole interactions has been the focus of attention for synthetic chemists. A novel chiral antimony cation/anion pair was utilized to catalyze the enantioselective transfer hydrogenation of benzoxazines with remarkable efficiency and enantiocontrol potency even at 0.05 mol % loading. Investigation into the properties of the catalyst and mechanistic insights were conducted through nonlinear effect studies, 1H NMR, LC-MS, and control experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Junxian Yang, Ji-Wei Zhang, Wen Bao, Sheng-Qi Qiu, Shaoyu Li, Shao-Hua Xiang, Jun Song, Junmin Zhang, Bin Tan
Summary: This study reports a new strategy for catalytic enantioselective construction of axially chiral B-aryl-1,2-azaborines, achieving efficient stereochemical control through multiple hydrogen bonding interactions. The reaction demonstrates high efficiency, excellent enantioselectivity, shortened reaction duration, and high practicality with scalable reaction and facile cleavage of N-N bond in the product.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: This paper describes the strategies to address the challenges in efficient synthetic access and skeletal variety within the organocatalytic context. The approaches include modulating nucleophilicity, designing electron-withdrawing activating groups, and using electrophilic arene precursors for arylation. These strategies have led to the synthesis of structurally diverse axially chiral compounds.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Pengquan Chen, Mei-Jun Lv, Jun Kee Cheng, Shao-Hua Xiang, Xiang-Zhong Ren, Junmin Zhang, Bin Tan
Summary: Azonaphthalenes have been confirmed as effective arylation reagents for various asymmetric transformations. In this study, a highly efficient approach to form triaryl-substituted all-carbon quaternary stereocenters through chiral phosphoric acid-catalyzed enantioselective arylation of 3-aryl-2-oxindoles with azonaphthalenes is revealed. This chemistry is scalable and demonstrates excellent functional group tolerance, providing a series of 3,3-disubstituted 2-oxindole derivatives in good yields with excellent enantiocontrol.
Article
Chemistry, Multidisciplinary
Si-Li Lin, Ye-Hui Chen, Huan-Huan Liu, Shao-Hua Xiang, Bin Tan
Summary: In this study, chiral cyclobutene units were synthesized using bicyclo[1.1.0]butanes for the first time, offering an efficient and asymmetric route with good regio- and enantiocontrol. Control experiments verified the formation of a key carbocation intermediate at the benzylic position.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Liang-Wen Qi, Shaoyu Li, Shao-Hua Xiang, Jun (Joelle) Wang, Bin Tan