Article
Chemistry, Physical
Amit Singh Adhikari, Soumen Pandit, Ruchir Kant, Nilanjana Majumdar
Summary: An efficient method for highly selective allylic substitution of vinylcyclopropanes using carboxylic acids via iridium catalysis has been developed, providing a high yield of synthetically useful chiral building blocks. The practical application of the products in useful transformations demonstrates its utility.
Article
Chemistry, Multidisciplinary
Pep Rojo, Medea Molinari, Albert Cabre, Clara Garcia-Mateos, Antoni Riera, Xavier Verdaguer
Summary: Chiral compounds containing nitrogen heteroatoms are crucial for the chemical, pharmaceutical, and agrochemical industries. In this study, a series of P-stereogenic phosphinooxazoline iridium catalysts were synthesized and successfully used in the asymmetric hydrogenation of N-Boc-2,3-diarylallyl amines, achieving high enantioselectivity. The synthetic utility of the obtained 2,3-diarylpropyl amines was also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ming Xu, Yizhao Ouyang, Linghua Wang, Shuai Zhang, Pengfei Li
Summary: A highly enantioselective and regioselective dearomative borylation method was developed for the synthesis of unprecedented heterocyclic alpha-amino boronates. The products can serve as useful intermediates for highly functionalized tetrahydroquinolines and cyclic alpha-aminoboronate derivatives.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Pablo Vazquez-Dominguez, Antonio Romero-Arenas, Rosario Fernandez, Jose Maria Lassaletta, Abel Ros
Summary: The catalytic hydroarylation of alkynes is a useful method for synthesizing functionalized alkenes with excellent control of regio- and stereochemistry. However, there is a scarcity of asymmetric methodologies in this field. In this study, an atroposelective Ir-catalyzed C-H hydroarylation of alkynes was developed, enabling the asymmetric synthesis of axially chiral heterobiaryl trisubstituted olefins with high yields and enantioselectivities up to 98% ee.
Article
Chemistry, Organic
Congcong Yin, Yingmin Pan, Longsheng Zheng, Bijin Lin, Jialin Wen, Xumu Zhang
Summary: Enantioselective hydrogenation of imines via an outer-sphere mechanism was achieved using an iridium tridentate catalyst, resulting in high enantioselectivities and turnover numbers up to 10,000. This method was successfully applied in the synthesis of chiral amines with an alpha-stereocenter, allowing for the preparation of cinacalcet with remarkably high enantioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Cong Fu, Xin Chang, Lu Xiao, Chun -Jiang Wang
Summary: In this study, a one-pot Cu-mediated H-D exchange using inexpensive heavy water as the deuterium source, followed by Cu- and Ir-catalyzed stereodivergent allylic alkylation, has been developed to efficiently access enantioenriched alpha-deuterium-labeled alpha-amino acids.
Article
Chemistry, Multidisciplinary
Yu Nie, Jing Li, Qianjia Yuan, Wanbin Zhang
Summary: In this work, we developed an iridium-catalyzed asymmetric hydrogenation of hydantoin and thiazolidinedione derived exocyclic alkenes using BiphPHOX as a ligand. The reaction showed excellent functional group tolerance and provided the hydrogenated products with high yields and enantioselectivities. Moreover, the hydrogenated product can be efficiently transformed into an intermediate for the synthesis of a HIV protease inhibitor.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Si-Yong Yin, Qiansujia Zhou, Chen-Xu Liu, Qing Gu, Shu-Li You
Summary: The iridium-catalyzed asymmetric C-H alkylation was used for the first time to construct N-N biaryl atropisomers. The method showed good yields (up to 98%) and excellent enantioselectivity (up to 99% ee) for the synthesis of axially chiral molecules based on indole-pyrrole skeleton. This method also allowed the synthesis of N-N bispyrrole atropisomers with high yields and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Aditya Chakrabarty, Santanu Mukherjee
Summary: The first enantioselective synthesis of alpha-allenylic amides and ketones through allenylic alkylation of vinyl azides is reported. The presence of a desiccant plays a crucial role in controlling the chemodivergency of this enantioconvergent and regioselective reaction. Utilizing racemic allenylic alcohols as the alkylating agent, the overall process represents a dynamic kinetic asymmetric transformation (DyKAT) where both the products are formed with the same absolute configuration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Tingting Liu, Zefei Xu, Jinhui Feng, Shanshan Yu, Min Wang, Peiyuan Yao, Qiaqing Wu, Dunming Zhu
Summary: Two enantiocomplementary imine reductases (IREDs) with high enantioselectivity were identified through screening and engineering, which allowed the synthesis of a series of 1-heteroaryl tetrahydroisoquinolines with high to excellent ee values and isolated yields, providing an effective method for constructing pharmaceutically important alkaloids, including the intermediate of kinase inhibitor TAK-981.
Article
Chemistry, Organic
Tingting Liu, Zefei Xu, Jinhui Feng, Shanshan Yu, Min Wang, Peiyuan Yao, Qiaqing Wu, Dunming Zhu
Summary: Two highly enantioselective enantiocomplementary imine reductases (IREDs) were discovered through screening and enzyme engineering, which exhibited catalytic activity towards the reduction of 1-heteroaryl dihydroisoquinolines. By utilizing (R)-IR141-L172M/Y267F and (S)-IR40, a series of different 1-heteroaryl tetrahydroisoquinolines were efficiently synthesized with excellent enantioselectivity (82 to >99% ee) and high isolated yields (80 to 94%), providing an effective method for constructing pharmaceutically important alkaloids, including the intermediate of kinase inhibitor TAK-981.
Article
Chemistry, Organic
Gregg A. Barcan, Doo-Hyun Kwon, Jiasheng Guo, John A. Kowalski, Li Liu, Mark Nilson, Jack Sisko, Huan Wang, Timothy A. Brown, Habib Gholipour-Ranjbar
Summary: Establishing the two stereocenters in the benzothiaze-pine ring of linerixibat (GSK2330672) has always been a long-standing problem at GSK. Our solution is based on an episulfonium-controlled Ritter reaction followed by a sulfoxide-directed reduction. Both steps are supported by literature precedent and computational experiments. Transition state modeling suggests that the sulfoxide-directed reduction proceeds through electronic repulsion between the lone pair of electrons on sulfur and the incoming borohydride anion.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Pusu Yang, Rui-Xiang Wang, Yuan-Zheng Cheng, Chao Zheng, Shu-Li You
Summary: This study describes an iridium-catalyzed asymmetric allylic benzylation reaction under light irradiation. 2-methylbenzophenone derivatives were activated by ultraviolet light, enabling high enantioselectivity without the use of strong bases or pre-activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xi-Jia Liu, Wen-Yun Zhang, Chao Zheng, Shu-Li You
Summary: Herein, an Ir-catalyzed asymmetric allylic substitution reaction of methyl azaarenes is reported. The reaction exhibits high yields and enantioselectivity, and utilizes the Knochel reagent for the formation of benzylic nucleophiles without additional activating reagents. The synthetic utility of this method has been demonstrated by an enantioselective synthesis of an allosteric protein kinase modulator.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
