Article
Chemistry, Multidisciplinary
Fabian Severin, Giovanni M. Fusi, Christina Wartmann, Jorg-Martin Neudoerfl, Albrecht Berkessel
Summary: In this study, we report a highly syn-selective epoxidation method for terminal allylic alcohols using a titanium salalen complex catalyst at room temperature and aqueous hydrogen peroxide as oxidant. The results demonstrate that enantiopure terminal allylic alcohols can be efficiently converted to epoxy alcohols with high yields and excellent syn-diastereoselectivity. This method shows great synthetic potential and is demonstrated by the gram-scale preparation of a tetrahydrofuran building block with three stereocenters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Fuad O. Usman, Achyut R. Gogoi, Jason C. Mixdorf, Osvaldo Gutierrez, Hien M. Nguyen
Summary: In this study, an enantioselective synthesis of 1,2-disubstituted allylic fluorides using a chiral diene-ligated rhodium catalyst was reported. Kinetic studies and calculations were conducted to investigate the molecular structure and reaction kinetics of the formation process of 1,2-disubstituted allylic fluorides. The reaction selectivity and yield of the construction process of 1,2-disubstituted allylic fluorides were also identified.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Thomas Q. Davies, John J. Murphy, Maxime Dousset, Alois Fuerstner
Summary: Nickel catalysis combined with cyclodiphosphazane or VAPOL-derived phosphoramidite ligands allows for the selective access to monoprotected vicinal diols through reductive coupling of dienol ethers and aldehydes. The observed regioselectivity is unprecedented, with the diene reacting at the least nucleophilic and most hindered C atom attached to the oxygen substituent. Notably, both syn and anti diastereomers of the products can be accessed with excellent diastereo- and enantioselectivity depending on the configuration of the diene partner.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yongjie Shi, Jingxin Wang, Qin Yin, Xumu Zhang, Pauline Chiu
Summary: An asymmetric 1,2-reduction of cyclic alpha,beta-unsaturated ketones was achieved under mild conditions, catalyzed by in situ generated copper hydride ligated with (R)-DTBM-C-3*-TunePhos. The reaction produced various enantiomerically enriched cyclic allylic alcohols, with up to 98% ee enantioselectivities for alpha-brominated cydoalkenones and moderate enantioselectivities for substrates without alpha-substituents.
Article
Chemistry, Organic
Ruiqi Tong, Song Liu, Chen Zhao, Dongyang Jiang, Lu Gao, Wanshu Wang, Bengui Ye, Zhenlei Song
Summary: A new nonracemic reagent has been developed for the asymmetric crotylboration of aldehydes. This reaction provides compounds with high yields and excellent stereo-selectivity, showcasing its potential in the synthesis of polyketide natural products.
Article
Chemistry, Multidisciplinary
Shubham Dutta, Akhila K. K. Sahoo
Summary: This paper describes a Pd-catalyzed three-component syn-1,2-arylmethylation method, which successfully synthesizes methyl-containing tetra-substituted olefins by using readily available and stable coupling partners iodo-arenes and methyl boronic acid. The reaction shows a broad scope with excellent functional-group tolerance and exhibits remarkable regio- and stereoselectivity. Biologically relevant motifs (BRM) bearing iodo-arenes and ynamides are also used for late-stage syn-1,2-arylmethylation of alkynes. Additionally, aryl-alkylation, aryl-trideuteriomethylation, alkynyl-methylation, and alkenyl-methylation of ynamides are presented, leading to the synthesis of synthetically important beta-amino-indenones and alpha-fluoro-alpha '-methyl ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Masa Sterle, Matej Hus, Matic Lozinsek, Anamarija Zega, Andrej Emanuel Cotman
Summary: Stereopure CF3-substituted syn-1,2-diols were synthesized through the reductive dynamic kinetic resolution of corresponding alkyl ketones, yielding products with >95% ee and >87:13 syn/anti ratio. This method provides a rapid access to stereopure bioactive molecules. Moreover, DFT calculations were conducted on three types of Noyori-Ikariya ruthenium catalysts to demonstrate their general ability to control stereoselectivity through hydrogen bond acceptor SO2 region and CH/pi interactions.
Article
Chemistry, Multidisciplinary
Zheng Tan, Long Chen, Lingyu Li, Yuzhen Li, Yao Luo, Fei Wang, Shunxi Dong, Xiaoming Feng
Summary: In this study, a practical and efficient synthesis of a-methylene-?-butyrolactones was developed using chiral N,N'-dioxide/Al-III complex as the catalyst. The key success of this transformation was the kinetic resolution of allylboration intermediate via asymmetric lactonization. Taking advantage of this method, a catalytic asymmetric total synthesis of eupomatilones 2, 5, and 6 was accomplished.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Benjamin Owen, Monica de Gaetano, Andrew Gaffney, Catherine Godson, Patrick J. Guiry
Summary: The researchers synthesized BCP-containing synthetic lipoxin A4 mimetics and found that one of them exhibited high anti-inflammatory activity.
Article
Chemistry, Multidisciplinary
Martin S. Maier, Andrej Shemet, Dirk Trauner
Summary: The 2'-phosphodiesterase inhibitor A-74528 is a complex type II polyketide with intriguing biosynthesis and unusual biological activity. This study focuses on the synthesis of A-74528, specifically the construction of its carbon skeleton and the installation of its stereocenters. The strategy involves various reactions to establish carbocycles and append the pyrone moiety.
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)
Article
Chemistry, Multidisciplinary
Xin Yu, Lingfei Hu, Wolfgang Frey, Gang Lu, Rene Peters
Summary: Catalytic allylic substitution is an important method in asymmetric synthesis to generate C-C bonds with enantioselectivity. However, a common limitation is the formation of allylic substitution products with (E)-configured C=C double bonds. In this study, a planar chiral palladacycle catalyst was used to achieve a diastereospecific reaction outcome, maintaining the C=C double bond geometry of the allylic substrates in highly enantioenriched products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Qing Li, Lin Li, Qiao-Ling Xu, Fei Pan
Summary: A general and mild method for radical acylation of [1.1.1]propellane with aldehydes has been developed, providing straightforward access to bicyclo[1.1.1]pentane ketones with a broad substrate scope. The synthetic utility of this methodology is demonstrated by the late-stage modification of bioactive molecules and the versatile transformation of bicyclo[1.1.1]pentane ketones, making it useful for drug discovery.
Article
Chemistry, Physical
Martin Pineiro-Suarez, Andres M. Alvarez-Constantin, Martin Fananas-Mastral
Summary: A catalytic asymmetric reaction involving allyl copper species with allylic gem-dichloride is reported, providing high selectivity chiral internal 1,5-dienes with (Z)-configured alkenyl boronate and alkenyl chloride. The synthetic utility of the products is demonstrated by synthesizing optically active compounds. DFT calculations reveal noncovalent substrate-ligand interactions accounting for the selectivity outcome.
Article
Chemistry, Multidisciplinary
Zeng-Hua Wu, Huai-Yu Wang, Huai-Lan Yang, Li-Hua Wei, Tamio Hayashi, Wei-Liang Duan
Summary: An iridium-catalyzed asymmetric synthesis of branched allylic phosphine compounds with excellent stereoselectivity and regioselectivity is reported. The use of phosphine sulfides with low deactivation capacity is crucial for the success of this reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
