Article
Chemistry, Organic
Fengyun Gao, Yifei Guo, Mengmeng Sun, Yalan Wang, Changyan Yang, Yuqiang Wang, Kairong Wang, Wenjin Yan
Summary: A novel difluoromethylated ketimine building block was synthesized for the first time by condensation of thioisatin and difluoroethylamine, providing efficient access to enantioenriched products with difluoroethylamine units. Further transformation of the intermediate led to the generation of versatile functional blocks while retaining the enantiomeric excess at the difluoromethyl-bound carbon.
Article
Chemistry, Organic
Nuermaimaiti Yisimayili, Hui Liu, Yun Yao, Chong-Dao Lu
Summary: Vicinal quaternary-tertiary carbon stereocenters were constructed with excellent stereoselectivity through aza-enolization and conjugate addition, showcasing a successful acyclic stereocontrol strategy. The facile stereodivergent synthesis of all four diastereomers of the Michael-type alkylation adducts was achieved by manipulating the absolute configuration of the sulfinyl group and/or the alpha-stereocenter in the ketimine.
Article
Chemistry, Multidisciplinary
Madhawee K. Arachchi, Richard N. Schaugaard, H. Bernhard Schlegel, Hien M. Nguyen
Summary: Asymmetric reactions that convert racemic mixtures into enantioenriched amines, especially those with a tetrasubstituted carbon stereocenter, are of great importance in pharmaceutical research. In this study, a chiral diene-ligated rhodium-catalyzed asymmetric substitution reaction was developed to efficiently prepare α-trisubstituted-α-tertiary amines containing pharmaceutically relevant secondary amine cores.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Jia-Le Zheng, Fei Liu, Xue Song, Zhi Zhao, Wei Du, Ying-Chun Chen
Summary: In this study, we found that dienones generated from the Morita-Baylis-Hillman carbonates of 2-cyclopentenone under Pd(0) catalysis could be umpolunged through pi-Lewis base activation to form regioselective eta 2-Pd(0) complexes, which then underwent asymmetric inverse-electron-demand oxa-Diels-Alder reaction with alpha-cyano chalcones. This study successfully constructed a range of fused pyran frameworks with dense substitutions and demonstrated excellent stereoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jianguo Yang, Saimei Liu, Jing Gui, Daokai Xiong, Jinshan Li, Zhiming Wang, Jun Ren
Summary: A highly selective hydroxyalkylation of aniline derivatives with arylglyoxal hydrates has been achieved using HFIP as a catalyst. The reaction provides efficient synthesis of various N,N-dialkylanilines and their derivatives with alpha-hydroxy carbonyl units under mild conditions. The method has shown great synthetic potential by enabling the facile synthesis of several structurally interesting molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Pingyang Wang, Pengcheng Du, Qianqian Sun, Jianhua Zhang, Hongmei Deng, Haizhen Jiang
Summary: The efficient silver-catalyzed decarboxylative radical allylation of alpha,alpha-difluoroarylacetic acids using allylsulfone as an allyl donor allows the successful allylation of these acids bearing various functional groups to access a series of 3-(alpha,alpha-difluorobenzyl)-1-propylene compounds in moderate to excellent yields under mild conditions. Experimental studies reveal that the alpha-fluorine substitution of arylacetic acid significantly influences free radical activity and reactivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Zheye Zhang, Jiaining Liu, Shang Gao, Bo Su, Ming Chen
Summary: We describe the stereoselective syntheses of (E)- and (Z)-crotylboronates with alpha,alpha-disubstitution. The alkylation reaction exclusively occurs at the alpha position to the boryl groups in the starting crotylboronates, resulting in the desired boronates while maintaining the original alkene geometries. The resulting alpha,alpha-disubstituted crotylboronates can undergo aldehyde addition to afford allylated products with high stereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Cheng Sheng, Zheng Ling, Yicong Luo, Wanbin Zhang
Summary: N,O-acetals are important building blocks for many synthetic intermediates, natural products, and pharmaceutical drugs. The authors developed a Cu-catalyzed asymmetric addition of alcohols to beta,gamma-alkynyl-alpha-imino esters, providing linear chiral N,O-ketals with high enantioselectivity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Mayuko Isomura, David A. Petrone, Erick M. Carreira
Summary: A robust catalytic system utilizing chiral Ir-phosphoramidite and La(OTf)(3) enables highly enantioselective alkylation reactions of racemic tertiary alpha-allenyl alcohols with tetrasubstituted silyl ketene acetals. The reaction displays broad functional group tolerance and allows efficient generation of beta-allenyl ester products with excellent enantioselectivity, which can be further upgraded in structural complexity via stereoselective metal-catalyzed functionalization reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Rikuo Hayashi, Kaori Ando, Taro Udagawa, Masahiro Sai
Summary: This study presents a method for synthesizing diverse beta-functionalized ketones from readily available 1-arylallylic alcohols in the presence of (trimethylsilyl)methylpotassium (TMSCH2K). The reaction proceeds via the formation of a highly nucleophilic dipotassio alpha,beta-dianion, which serves as a metal homoenolate equivalent and allows the one-pot synthesis of alpha,beta-difunctionalized ketones.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Xiang Pu, Qiu-Di Dang, Lei Yang, Xia Zhang, Dawen Niu
Summary: The authors report a doubly-stereoconvergent, Cu/Mg-catalyzed asymmetric propargylic substitution reaction that can selectively construct products with vicinal congested stereocenters. This reaction uses readily available starting materials, environmentally friendly catalysts, and has a broad substrate scope.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Akshi Tyagi, Sunita Mondal, Anmol, Vikas Tiwari, Tarak Karmakar, Subrata Kundu
Summary: The research demonstrates that the hydroamination of electron-deficient olefins can be efficiently carried out using the (CAAC)Cu-Cl catalyst at room temperature and under an open atmosphere, and the catalyst also shows excellent efficiency in the hydroaryloxylation and hydroalkoxylation of alkenes. Detailed computational studies reveal that the reaction proceeds via either a four-membered or a six-membered cyclic transition state containing the copper ion.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Dequan Zhang, Jialin Wen, Xumu Zhang
Summary: The construction of chiral quaternary carbon stereocenters has been a long-standing challenge in organic chemistry. In this study, a hydroformylation approach was reported to access chiral quaternary stereogenic centers, and a variety of chiral alpha-quaternary amino acids could be synthesized. The regioselectivity was found to be influenced by the electronic properties of the substituents, and a substrate-catalyst interaction model was proposed based on the chiral environment of the rhodium/Yanphos complex.
Article
Chemistry, Multidisciplinary
Xiaoyun Wu, Wei Ma, Weijun Tang, Dong Xue, Jianliang Xiao, Chao Wang
Summary: A Fe-catalyzed amidation of allylic alcohols with chiral tert-butylsulfinamide has been developed for the synthesis of chiral sulfinamide olefin derivatives. The reaction proceeds under mild conditions with water as the only by-product.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Shiru Yuan, Wen-Hua Zheng
Summary: The study demonstrated the isothiourea-catalyzed enantioselective construction of tertiary alpha-fluoro stereogenic centers using branched alkynyl-substituted acetic acids as starting materials, achieving a broad range of optically active tertiary alpha-alkyl fluorides with high enantioselectivity (up to 97% ee). Moreover, this methodology was successfully scaled up to a Gram scale without loss of enantioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ana Bahamonde, Paolo Melchiorre
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2016)
Article
Chemistry, Multidisciplinary
Ana Bahamonde, John J. Murphy, Marika Savarese, Eric Bremond, Andrea Cavalli, Paolo Melchiorre
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Chemistry, Multidisciplinary
Sandeep R. Kandukuri, Ana Bahamonde, Indranil Chatterjee, Igor D. Jurberg, Eduardo C. Escudero-Adan, Paolo Melchiorre
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2015)
Article
Chemistry, Multidisciplinary
Elena Arceo, Ana Bahamonde, Giulia Bergonzini, Paolo Melchiorre
Article
Chemistry, Multidisciplinary
Jamie R. Allen, Ana Bahamonde, Yukino Furukawa, Matthew S. Sigman
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Multidisciplinary Sciences
Brittany C. Haas, Adam E. Goetz, Ana Bahamonde, J. Christopher McWilliams, Matthew S. Sigman
Summary: The study developed statistical models correlating measured rates with physical organic descriptors to predict reaction rates for untested carboxylic acid/amine pairs. By developing an end-to-end data science-based workflow to select appropriately distributed coupling partners in chemical space, the study facilitated the development of statistical models.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Organic
Jason P. Hibbard, Jessalyn G. Yam, Eyad B. Alsalek, Ana Bahamonde
Summary: A mild sustainable protocol has been developed to couple primary alkyl chlorides and bromides with amides, allowing access to a remarkably orthogonal scope without the need for strongly basic conditions, high temperatures, or organometallic catalysts. K3PO4 is used to facilitate the formation of secondary and tertiary amides, with alkylated amide products obtained in good to excellent yields, showing no substantial limitations based on the steric and electronic properties of the coupling partners.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Robert D. Bradley, Ana Bahamonde
Summary: This paper describes a mild strategy to promote amide arylations by proposing photoinduced oxidation of a Ni(II) aryl amido intermediate to facilitate the challenging C-N reductive elimination step at moderate temperatures. The use of mildly basic conditions enables a broad scope of reactions, including protected amino acids, heterocycles, phenols, and sterically hindered substituents. Therefore, this work presents an attractive strategy to enable late-stage functionalization of pre-existing amide moieties in commercial drugs and natural products.
Review
Chemistry, Multidisciplinary
Ana Bahamonde
Summary: This review focuses on the development of asymmetric variants of palladium-catalyzed alkene functionalization, highlighting the challenges faced by different substrate classes and the strategies and methods used to overcome them. New methodologies for various reactions are discussed, with a special emphasis on the progression from cyclic to acyclic to electronically unbiased olefin substrates.
TRENDS IN CHEMISTRY
(2021)