Article
Chemistry, Organic
Rodney A. Fernandes, Naveen Chandra, Ashvin J. Gangani, Gulenur N. Khatun
Summary: An efficient method for the synthesis of (E)-(3-alkoxybut-1-enyl)benzenes has been developed via Pd-catalyzed regioselective intermolecular hydroalkoxylation of 1-arylbutadienes. This method offers a simple operation, without the need for dry reaction conditions, and shows good tolerance to various substrates. The presence of chloromethyl methyl ether (MOMCl) as an additive is crucial to the success of the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ge-Yun You, Xiao-Feng Liu, Pei-Wen Fang, Lu-Fang Liang, Cheng-Hao Dai, Bin Feng
Summary: A study on the activity of chiral sulfinyl imine-thioether ligands in Pd-catalyzed asymmetric allylic alkylation reaction reveals the significant effect of the structure of sulfinamide motifs on the reaction yield and enantiomeric excess.
Article
Chemistry, Organic
Takashi Mino, Yohei Fujisawa, Shizuki Yoshida, Mitsuru Hirama, Takumu Akiyama, Ryo Saito, Yasushi Yoshida, Yoshio Kasashima, Masami Sakamoto
Summary: By synthesizing cinnamoyl amide type chiral P,olefin ligand (S)-4, separable diastereomers of 4d were obtained successfully, and asymmetric allylic substitution reactions of indoles using (S,aS)-4d as a chiral ligand demonstrated high enantioselectivities (up to 98% ee).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Takashi Mino, Kaho Takaya, Kaito Koki, Natsume Akimoto, Yasushi Yoshida, Yoshio Kasashima, Masami Sakamoto
Summary: We synthesized N-alkyl-N-cinnamoyl amide type phosphine-olefin compounds 1 and observed axial chirality in the C(aryl)-N(amide) bond of compounds 1 using HPLC analysis with a chiral stationary phase column. Enantiomeric isomers of 1 were obtained and (-)-1 was demonstrated as a chiral ligand in Pd-catalyzed asymmetric allylic substitution reactions, leading to high enantioselectivity (up to 97% ee) in the esterification process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Eleanor Bowen, Gillian Laidlaw, Bethany C. Atkinson, Timur A. McArdle-Ismaguilov, Vilius Franckevicius
Summary: In this study, a palladium-catalyzed decarboxylative asymmetric allylic alkylation reaction was developed to access enantioenriched heterocyclic sulfones. The reaction showed high levels of enantioselectivity and provided a new pathway for the synthesis of stereodefined cyclic sulfones for medicinal chemistry applications.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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
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
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, Inorganic & Nuclear
Pol de la Cruz-Sanchez, Maria Biosca, Marc Magre, Jorge Faiges, Jessica Margalef, Oscar Pamies, Montserrat Dieguez
Summary: High enantioselectivities and activities were achieved in the Pd-catalyzed allylic substitution reaction using a family of adaptable ligands. The ligands demonstrated high performance in various catalytic processes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(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)
Article
Chemistry, Multidisciplinary
Yongzhuo Xu, Jiajia Wang, Guo-Jun Deng, Wen Shao
Summary: The significance of chiral alpha-tertiary amines in medicinal chemistry and drug development has been well-established in the last few decades. These compounds have attractive structural motifs and are preclinical candidates for various applications. Synthetic methods for their assembly have been extensively studied, leading to the development of new strategies for enantioselective construction of chiral alpha-tertiary amines via transition-metal catalysis.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Yeosan Lee, Seungcheol Han, Seung Hwan Cho
Summary: Chemical and stereoselective transformations of polyborylalkanes are powerful methods to access optically active molecules efficiently. Gem-diborylalkanes, as versatile synthetic handles, can generate key intermediates for various enantioselective reactions. Catalytic reactions using gem-diborylalkanes can rapidly access diverse enantioenriched organoboron compounds for further transformations.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Review
Chemistry, Multidisciplinary
David Laws III, Christopher D. Poff, Ethan M. Heyboer, Simon B. Blakey
Summary: Planar chirality is an important form of molecular chirality that can induce enantioselectivity in transition metal catalysts. However, there are limitations in using late transition metal planar chiral complexes for enantioselective transformations due to synthetic constraints. Additionally, the methods for stereochemical assignment of planar chiral compounds are sometimes conflicting. This review aims to provide clarity on the assignment methods and overview the synthesis and use of late transition metal planar chiral complexes as enantioselective catalysts.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Hao-Dong Qian, Zhi-Heng Li, Shuang Deng, Chaochao Yao, Hua-Ming Xiang, Guang Xu, Zi-Qi Geng, Zihao Wang, Linfeng Chen, Chunrong Liu, Cuiju Zhu, Xiaotian Qi, Hao Xu
Summary: Distinct regio- and enantioselectivity control has been achieved in copper-catalyzed vinylogous and bisvinylogous propargylic substitution using a novel chiral N,N,P ligand. The developed method provides an efficient and selective approach to the synthesis of enantioenriched alkynyl unsaturated carbonyl compounds, with excellent functional group tolerance and broad substrate scope. The synthetic utility of the developed method is demonstrated by gram-scale synthesis and application to the enantioselective synthesis of challenging compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Chao Xia, Dong-Chao Wang, Gui-Rong Qu, Hai-Ming Guo
Summary: A highly enantioselective allylation reaction of vinylethylene carbonate by asymmetric palladium catalysis has been developed for various N-heteroaromatic substrates. The efficient synthesis of acyclic nucleoside analogs with high yields (up to 96%) and enantioselectivities (up to 99%) was demonstrated with only 0.5 mol% of Pd catalyst. Additionally, these acyclic nucleosides can undergo rapid transformation into a variety of structurally diverse chiral acyclic nucleosides and isonucleosides.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Jessica Margalef, Maria Biosca, Pol de la Cruz-Sanchez, Xisco Caldentey, Carles Rodriguez-Escrich, Oscar Pamies, Miquel A. Pericas, Montserrat Dieguez
Summary: A family of phosphite/phosphinite-thioether ligands has shown excellent catalytic performance in the Ir-catalyzed asymmetric hydrogenation of a variety of olefins. Their modular architecture allows for a broad substrate scope, covering different substitution patterns and functional groups. The catalytic performance of the Ir-ligand assemblies remains consistent when using environmentally friendly 1,2-propylene carbonate as a solvent.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Oscar Pamies, Jessica Margalef, Santiago Canellas, Jinju James, Eric Judge, Patrick J. Guiry, Christina Moberg, Jan-E Backvall, Andreas Pfaltz, Miquel A. Pericas, Montserrat Dieguez
Summary: This review covers the evolution, mechanistic understanding, and recent advances in enantioselective Pd-catalyzed allylic substitution, decarboxylative, and oxidative allylic substitutions. The catalytic data and examples of their application are collected, along with discussions on key mechanistic aspects for high selectivity and comparison with other metals. Different nucleophiles employed and ligand types for improved results in asymmetric allylic substitutions are highlighted.
Review
Chemistry, Multidisciplinary
Montserrat Dieguez, Oscar Pamies, Christina Moberg
Summary: Biological systems inspire the design of synthetic catalysts which enhance chemical selectivity through optimized molecular recognition interactions. Catalytic systems that adapt to changing environments can accommodate a wide range of substrates, increasing versatility.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Review
Chemistry, Inorganic & Nuclear
Jessica Margalef, Maria Biosca, Pol de la Cruz Sanchez, Jorge Faiges, Oscar Pamies, Montserrat Dieguez
Summary: The success of phosphine-oxazoline ligands has led to advancements in P-oxazoline ligand families, resulting in diverse structures and more efficient ligands for asymmetric transformations. Through proper design, these heterodonor bidentate ligand families exhibit superior catalytic performance in a variety of asymmetric reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Pol de la Cruz-Sanchez, Maria Biosca, Marc Magre, Jorge Faiges, Jessica Margalef, Oscar Pamies, Montserrat Dieguez
Summary: High enantioselectivities and activities were achieved in the Pd-catalyzed allylic substitution reaction using a family of adaptable ligands. The ligands demonstrated high performance in various catalytic processes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Jessica Wahlers, Jessica Margalef, Eric Hansen, Armita Bayesteh, Paul Helquist, Montserrat Dieguez, Oscar Pamies, Olaf Wiest, Per-Ola Norrby
Summary: The transition state force field (TSFF) derived by the quantum-guided molecular mechanics (Q2MM) method can be used to rapidly screen ligand/substrate combinations, revealing multiple cases of computationally predicted major enantiomer differing from the experimentally observed one in literature reactions.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Maria Biosca, Pol de la Cruz-Sanchez, Daniel Tarr, Patricia Llanes, Erik A. Karlsson, Jessica Margalef, Oscar Pamies, Miquel A. Pericas, Montserrat Dieguez
Summary: A chiral phosphine-triazole ligand has been developed for the Ir-catalyzed asymmetric hydrogenation of exocyclic benzofused alkenes, which overcomes previous limitations and exhibits excellent enantioselectivity. The catalyst shows good tolerance towards various substituents and substitution patterns at both aromatic rings, making it an effective tool for hydrogenation of exocyclic olefins.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Joan Salto, Maria Biosca, Oscar Pamies, Montserrat Dieguez
Summary: A set of complex tricyclic compounds containing multiple functional groups and stereogenic centers has been synthesized in only two steps with excellent diastereo- and enantioselectivities, using a highly versatile and enantioselective Pd-catalyzed reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Maria Biosca, Pol de la Cruz-Sanchez, Jorge Faiges, Jessica Margalef, Ernest Salomo, Antoni Riera, Xavier Verdaguer, Joan Ferre, Feliu Maseras, Maria Besora, Oscar Pamies, Montserrat Dieguez
Summary: Ir-MaxPHOX-type catalysts exhibit high catalytic performance in the hydrogenation of a wide range of nonchelating olefins with different geometries, substitution patterns, and degrees of functionalization. These air-stable and readily available catalysts have been successfully used in the asymmetric hydrogenation of di-, tri-, and tetrasubstituted olefins (ee ' s up to 9996). The combination of theoretical calculations and deuterium labeling experiments has revealed the factors responsible for the observed enantioselectivity, allowing for the rationalization of suitable substrates for these Ircatalysts.
Article
Chemistry, Organic
Maria Biosca, Daniel Tarr, Oscar Pamies, Montserrat Dieguez
Summary: Pd-catalyzed asymmetric allylic substitution (AAS) is an effective method for producing chiral molecules with alkene-substituted frameworks. Phosphite-oxazolines have emerged as strong candidates to be privileged ligands, providing high enantiocontrol in the Pd-AAS of various substrates and nucleophiles. This review discusses the progress made in the design of tailor-made phosphite-oxazoline ligand libraries for the Pd-AAS and its application in the construction of chiral complex molecules.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
