Article
Chemistry, Multidisciplinary
Saikat Das, Qiupeng Hu, Azusa Kondoh, Masahiro Terada
Summary: Enantioselective protonation of diarylphosphine oxides with 2-vinyl azaheterocycle N-oxide derivatives was achieved using chiral bis(guanidino)iminophosphorane as the catalyst, where a chiral weak conjugate acid played a crucial role as the proton source. This method allows for a broadening of enantioselective reaction systems by utilizing less acidic pronucleophiles, and enables the synthesis of chiral metal complex ligands through reduction of phosphine oxide and N-oxide units.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xinduo Sun, Chaoji Xiong, Fanrui Zhou, Kun Liang, Chunhua Wu, Xiaoping Rao, Qian Chen
Summary: The asymmetric addition of terminal alkynes catalyzed by a transition metal to isatins is an efficient and economical method for synthesizing 3-alkynyl-3-hydroxy-2-oxindoles. Using a new dimeric chiral quaternary ammonium derived from quinine as the cationic inducer, under mild conditions, the desired chiral compounds can be obtained in good to high yields with high enantioselectivity (<= 99% ee), and a variety of aryl-substituted terminal alkynes and substituted isatins are tolerated in this reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
David A. McLeod, Mathias Kirk Thogersen, Casper Larsen Barlose, Mette Louise Skipper, Erlaitz Basabe Obregon, Karl Anker Jorgensen
Summary: This study presents a novel enantioselective (8+3) cycloaddition reaction using a chiral bifunctional Bronsted base catalyst. The reaction leverages an anionic activation strategy and differs from typical Lewis-acid activation protocols. Experimental and computational results support the relevance of this reaction and its potential application in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Jianwen Jin, Lorenzo Carli, Yichao Zhao, Xuehua Zhu, Bo Xia, Philip Wai Hong Chan
Summary: This study presents a synthetic method for efficiently preparing enantioenriched secondary and tertiary 3-amido allylic alcohols. By utilizing stereoablative enantioselective kinetic resolution (KR) catalyzed by a chiral Brønsted acid, the researchers achieved product yields up to 50%, with ee and s values exceeding 99% and >200, respectively. The developed divergent catalytic protocol demonstrated excellent functional group tolerance and was further exemplified by the preparation of one tertiary example on a 1 mmol scale, followed by reduction or bromination to yield corresponding 1,3-amino alcohol and 2-bromo-1,3-amino alcohol derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Zara M. Seibel, Jeffrey S. Bandar, Tristan H. Lambert
Summary: The enantioselective synthesis of alpha-substituted glutamates and pyroglutamates via a cyclopropenimine-catalyzed Michael addition of amino ester imines has been described, achieving enantioselectivities of up to 94% and compatibility with various functional groups. The impact of catalyst structure and imine substitution was discussed, highlighting a broader and more enantioselective access to pyroglutamate derivatives compared to other methods.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
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, Organic
Jiadong Tang, Can Chen, Tao Hong, Zibin Zhang, Chunsong Xie, Shijun Li
Summary: Supramolecular asymmetric catalysis is an important field that combines supramolecular chemistry and asymmetric catalysis. By utilizing crown ether-based host-guest chemistry and chiral phosphoric acid, the catalytic reaction can be regulated, leading to improved yield and enantioselectivity of the catalyst.
Article
Chemistry, Multidisciplinary
En Li, Jiean Chen, Yong Huang
Summary: The Michael reaction is an important method for preparing functional molecules with a β-stereogenic center. However, the enantioselective seleno-Michael addition is still poorly explored. In this study, a highly enantioselective Michael addition reaction of alkyl selenols to enones was reported, introducing a Se atom asymmetrically to an electron-deficient double bond. A chiral bifunctional N-heterocyclic carbene (NHC)/thiourea catalyst was developed and showed remarkable selectivity in delivering chiral β-seleno ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Hao Zhang, Xian He, Xiang-Ai Yuan, Shouyun Yu
Summary: Expanding the discovery of biologically or pharmacologically active molecules can be achieved by transforming chemical space into three-dimensional space through stereospecific reactions. This study focuses on alkene subunits as ubiquitous structural motifs and inexpensive starting points for this purpose. A kinetic resolution method enabled by photoexcited chiral copper complex-mediated alkene E -* Z isomerization was disclosed, which allowed for the enantiodivergent synthesis of 2-cinnamylpyrrolines. Mechanistic experiments and DFT calculations revealed the reasons for the observed kinetic resolution efficiency, which is due to the different association abilities between two enantiomers and the chiral copper complex in the ground state (thermodynamics) and the different overall sensitization rates of the substrate-catalyst complex in the excited state (kinetics). This revitalized protocol of kinetic resolution shows wide functional group compatibility and enables the exploration of three-dimensional chemical space, thereby providing an advanced and complementary method for stereochemistry control in triplet-state photoreactions.
Article
Chemistry, Multidisciplinary
Jia-Bin Pan, Zhi-Chun Yang, Xuan-Ge Zhang, Mao-Lin Li, Qi-Lin Zhou
Summary: Here, we present a method for enantioselective phosphoric acid catalyzed amination of ketenes generated from α-aryl-α-diazoketones. Mechanistic studies elucidated the reaction pathway and explained how the catalyst expedited the transformation and controlled the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Xiaoxiao Song, Yanjun Fan, Zhiming Zhu, Qijian Ni
Summary: We have developed a highly straightforward strategy for the synthesis of a new axially chiral 3-arylindolizine scaffold using chiral phosphoric acid catalyst. The reaction showed good scalability and yielded a series of axially chiral 3-arylindolizines with excellent enantioselectivity. This approach not only has a broad substrate scope and mild reaction conditions, but also demonstrates the potential utility of the formed axially chiral compounds.
Article
Chemistry, Organic
Yongbiao Guo, Zhenhua Gao, Junchen Li, Xiaojing Bi, Enxue Shi, Junhua Xiao
Summary: This study presents a highly efficient and practical method for the direct synthesis of 2,3-dihydroquinazolinones from diverse aldehydes with excellent yields and enantioselectivity. The method shows improved enantioselectivity for aliphatic aldehydes and wide tolerance to different functional groups. Gram-scale synthesis and simplified work-up procedure demonstrate the practicality of this method.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ronghua Zhang, Shulin Ge, Jianwei Sun
Summary: SPHENOL is a new chiral framework with combined advantages of BINOL and SPINOL, serving as a platform for the development of chiral ligands and catalysts. Its superior performance has been demonstrated in mechanistically unrelated reactions, including hydrogenation, hydroacylation, and spirocyclization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Xi Gao, Chengwen Li, Li Chen, Xin Li
Summary: A highly enantioselective arylation reaction of 3-aryl-5-aminopyrazoles and quinone derivatives was achieved using a chiral phosphoric acid catalyst under mild conditions. The reaction showed a broad scope in terms of both arylation reaction partners and produced axially chiral arylpyrazoles with high yields (up to 95%) and enantioselectivity (99%). The reaction was proven to be efficient, as the catalyst loadings could be reduced to 1 mol % while maintaining enantioselectivity. Moreover, the synthetic utility of the protocol was demonstrated through gram-scale reaction and product transformation.
Article
Chemistry, Multidisciplinary
Xianghong Xu, Lingzi Peng, Xihao Chang, Chang Guo
Summary: The highly enantioselective O-propargylation catalyzed by combining a phosphine-nickel complex and an axially chiral sodium dicarboxylate offers a mild reaction conditions, broad substrate scope, and excellent functional group tolerance, leading to efficient synthesis of an array of enantioenriched compounds. The mechanistic studies support the role of the chiral carboxylate as a counterion for nickel catalysis, enabling the discovery of highly stereoselective transformations, showcasing its power in the asymmetric total synthesis of potent firefly luciferase inhibitors and (S)-dihydroyashabushiketol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Yujing Zhou, Jeffrey S. Bandar, Stephen L. Buchwald
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Chemistry, Multidisciplinary
Michael W. Gribble, Michael T. Pirnot, Jeffrey S. Bandar, Richard Y. Liu, Stephen L. Buchwald
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Chemistry, Multidisciplinary
Chaosheng Luo, Jeffrey S. Bandar
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Multidisciplinary
Yujing Zhou, Jeffrey S. Bandar, Richard Y. Liu, Stephen L. Buchwald
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Multidisciplinary
Juri Litterscheidt, Paul Judge, Andrea Buehlmeyer, Korinna Bader, Jeffrey S. Bandar, Tristan Lambert, Sabine Laschat
Article
Chemistry, Multidisciplinary
Thomas R. Puleo, Alivia J. Strong, Jeffrey S. Bandar
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Chaosheng Luo, Jeffrey S. Bandar
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Juri Litterscheidt, Jeffrey S. Bandar, Max Ebert, Robert Forschner, Korinna Bader, Tristan H. Lambert, Wolfgang Frey, Andrea Buehlmeyer, Marcus Braendle, Finn Schulz, Sabine Laschat
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Review
Chemistry, Multidisciplinary
Thomas R. Puleo, Stephen J. Sujansky, Shawn E. Wright, Jeffrey S. Bandar
Summary: The Concept article discusses recent applications of commercial organic superbases in modern synthetic methodologies, highlighting the advantages of organic superbases in discovering new base-catalyzed reactions, optimizing reactions that require stoichiometric Bronsted base, and in high-throughput experimentation technology.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Thomas R. Puleo, Danielle R. Klaus, Jeffrey S. Bandar
Summary: A new method is reported for the direct C-H etherification of N-heteroarenes under basic conditions, using potassium tert-butoxide as a catalyst and 2-halothiophenes as a reagent for halogen transfer. This protocol allows for regioselective oxidative coupling of alcohols with a variety of N-heteroarenes, such as 1,3-azoles, pyridines, diazines, and polyazines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Tyler W. Reidl, Jeffrey S. Bandar
Summary: The Lewis basic salts facilitate the coupling of benzyltrimethylsilane with (hetero)aryl nitriles, sulfones, and chlorides, providing a new route to 1,1-diarylalkanes with high selectivity. This method shows great potential in the synthesis of pharmaceutical analogues and multicomponent reactions, offering a complementary scope to existing methods.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Chaosheng Luo, Juan V. Alegre-Requena, Stephen J. Sujansky, Spencer P. Pajk, Liliana C. Gallegos, Robert S. Paton, Jeffrey S. Bandar
Summary: This study investigates the mechanism of nucleophilic addition of alcohols to simple alkenes, revealing the influence of alcohol stoichiometry on reaction rate and proposing a new solution. The improved method does not require excess alcohol, expands the substrate scope, and utilizes more practical catalyst systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Leidy V. Hooker, Jeffrey S. Bandar
Summary: This article summarizes the development and application of C-F bonds, focusing on the advantages of defluorination reactions in small molecule synthesis and illustrating how defluorofunctionalization can streamline synthesis and enable new reactions. The goal of the article is to educate chemists on the opportunities available for incorporating C-F bonds and exploiting their unique mechanistic pathways.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Spencer P. Pajk, Zisong Qi, Stephen J. Sujansky, Jeffrey S. Bandar
Summary: The base-catalyzed addition of 1-cyclopropylethanol to styrene derivatives with an acidic reaction workup enables anti-Markovnikov hydration. This method allows for the hydration of various styrene derivatives, including electron-deficient, ortho-substituted and heteroaryl variants. It offers an alternative route to terminal alcohols that avoids stoichiometric reduction and oxidation processes, demonstrating its utility in multigram scale reactions and a two-step hydration/cyclization process for the preparation of 2,3-dihydrobenzofuran derivatives.
Article
Chemistry, Multidisciplinary
Thomas R. Puleo, Jeffrey S. Bandar