Article
Chemistry, Organic
Tushar Janardan Pawar, Liliette Barcelona-Cazanave, Israel Bonilla-Landa, Magdalena Escobar, J. Oscar C. Jimenez-Halla, Alma Altuzar-Molina, Patricia Romero-Arellano, Andrew J. F. Edmunds, Martin Aluja, Jose Luis Olivares-Romero
Summary: This study presents a highly efficient iridium-catalyzed asymmetric hydrogenation approach for the total synthesis of biologically active (R,L) A. ludens host marking pheromone (HMP). The use of a novel Ir(i)-complex and a chiral P,N-ligand resulted in excellent enantioselectivities of up to 94% ee. The streamlined synthetic route involving seven reaction steps offers improved efficiency and shorter synthesis timelines compared to previous methods.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Wei Zhao, Wenji Wang, Huan Zhou, Qishan Liu, Zhiqing Ma, Haizhou Huang, Mingxin Chang
Summary: A one-pot asymmetric hydrogenation of pyridines with subsequent N-alkylation using a traceless Bronsted acid activation strategy is reported. The reaction exhibits high stereoselectivity and can be used to synthesize indolizidines and quinolizidines. Experimental and theoretical studies reveal that chloride anion and noncovalent interactions play important roles in determining the stereoselectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Yin-Feng Ma, Chuan-Jin Hou, De-Quan Wei, Xinwei He, Ting-Ting Chu, Xiu-shuai Chen, Xiang-Ping Hu
Summary: The asymmetric hydrogenation of beta-ketophosphonates with chiral Ir/P,N,N-ligands catalyst leads to high yields of beta-hydroxyphosphonates with good or excellent enantioselectivities under mild conditions.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Bram B. C. Peters, Norman Birke, Luca Massaro, Pher G. Andersson
Summary: The catalytic asymmetric hydrogenation of olefins is a powerful method for synthesizing chiral compounds. By using an iridium N,P-complex catalyst, various prochiral unsaturated amides can be efficiently reduced with high enantioselectivities. The attractive features of this method include its application in the synthesis of fenpropidin and the potential use of isomeric mixtures as starting materials.
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, 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
Pep Rojo, Agusti Lledos, Antoni Riera, Xavier Verdaguer
Summary: A threonine-derived phosphine-oxazoline iridium catalyst with excellent selectivity in the hydrogenation of N-Boc-2,3-diarylallylamines is reported. The reversible cyclometallation process and the influence of substitution at the phenyl group of the oxazoline on this equilibrium are thoroughly investigated. X-Ray analysis reveals the coordination mode of the cyclometallated tridentate ligand. Furthermore, the utilization of Ir(III) pre-catalysts or Ir(I)/Ir(III) mixtures in hydrogenation reactions is proposed based on the observed equilibrium dynamics.
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, 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)
Review
Biochemistry & Molecular Biology
Devalina Ray, Suman Majee, Ram Naresh Yadav, Bimal Krishna Banik
Summary: The asymmetric reactions of imines have attracted significant attention. However, the stereoselective reactions of N-phosphonyl/phosphoryl imines have been less explored. Chiral auxiliary-based asymmetric-induction strategy and the utilization of optically active ligands and metal catalysts have been successfully used to access various chiral amine scaffolds. This review critically summarizes the literature precedence of more than a decade and highlights the achievements and drawbacks in this area.
Article
Chemistry, Organic
Zi-Hao Jia, Ling-Yan Chen, Hao Zheng, Zhang-Rui Li, Qing-Chun Song, Ya Li
Summary: The study presents a successful synthesis of a series of chiral diarylmethylamines through the BINOL-derived DSI-catalyzed enantioselective aza-Friedel-Crafts reaction. The reaction provides a useful protocol for the direct synthesis of diarylmethylamine derivatives with good yields and excellent enantioselectivities (up to 97% ee).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Amanda L. Kwan, Robert H. Morris
Summary: This article introduces the largest-scale asymmetric catalytic process for the industrial production of (S)-metolachlor, which is achieved through the hydrogenation of N-(2-ethyl-6-methylphenyl)-1-methoxypropan-2-imine. The authors propose a plausible proton-first, outer-sphere mechanism based on density functional theory calculations that explains the reduction of the sterically hindered bond in the imine.
Article
Chemistry, Multidisciplinary
Haibo Wu, Hao Su, Erik J. Schulze, Bram B. C. Peters, Mark D. Nolan, Jianping Yang, Thishana Singh, Marten S. G. Ahlquist, Pher G. Andersson
Summary: The study presents a highly efficient desymmetrization of 1,4-dienes through iridium-catalyzed site- and enantioselective hydrogenation, allowing the installation of two adjacent stereogenic centers. High yields and excellent selectivities were achieved for a range of substrates, and the methodology was demonstrated by synthesizing key intermediates of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yulong Zhang, Peichao Zhao, Shengnan Sun, Qian Wu, Enxue Shi, Junhua Xiao
Summary: The authors developed a camphor-derived 2,3-diol as a chiral template to synthesize diverse P(III) and P(V) chiral compounds, which are highly desirable for asymmetric catalysis in organic chemistry.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Juana M. Perez, Roxana Postolache, Marta Castineira Reis, Esther G. Sinnema, Denisa Vargova, Folkert de Vries, Edwin Otten, Luo Ge, Syuzanna R. Harutyunyan
Summary: Chiral Mn(I) complexes have been shown to activate H-P bonds, providing a general method for the hydrophosphination of internal and terminal alpha,beta-unsaturated nitriles. Metal-ligand cooperation, a previously unconsidered strategy for catalytic H-P bond activation, plays a key role in the mechanistic action of the Mn(I)-based catalyst. Computational studies support a stepwise mechanism for the hydrophosphination reaction and offer insights into the origin of enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Llorenc Benavent, Alejandro Baeza, Megan Freckleton
Review
Chemistry, Organic
Megan Freckleton, Alejandro Baeza, Llorenc Benavent, Rafael Chinchilla
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2018)
Review
Chemistry, Physical
Diego A. Alonso, Alejandro Baeza, Rafael Chinchilla, Cecilia Gomez, Gabriela Guillena, Isidro M. Pastor, Diego J. Ramon
Editorial Material
Biochemistry & Molecular Biology
Alejandro Baeza
Article
Chemistry, Organic
Natalia Llopis, Alejandro Baeza
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Natalia Llopis, Patricia Gisbert, Alejandro Baeza
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Biochemistry & Molecular Biology
Natalia Llopis, Alejandro Baeza
Article
Chemistry, Applied
Natalia Llopis, Patricia Gisbert, Alejandro Baeza
Summary: The use of HFIP solvent in the oxidative cleavage of indoles results in higher yields of 2-ketoacetanilides, and it is also suitable for oxidation of various pyrroles and furans derivatives. The sustainable and practical nature of HFIP is demonstrated by its successful recycling up to 4 cycles in larger-scale reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Natalia Llopis, Patricia Gisbert, Alejandro Baeza, Jara Correa-Campillo
Summary: This study describes the oxidative dehydrogenation of N-heterocyclic compounds using H2O2 as an oxidant in combination with polar solvents such as 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and H2O. The best yields for heteroaromatic compounds were generally achieved in HFIP, but it is surprising that using a non-toxic solvent like H2O also gave good yields. Additionally, this method can be implemented on a larger scale and the HFIP solvent can be reused.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Adrian Moreno Gonzalez, Kieran Nicholson, Natalia Llopis, Gary S. Nichol, Thomas Langer, Alejandro Baeza, Stephen P. Thomas
Summary: In this study, high oxidation-state carbonyl coupling partners were reacted with enones using two-fold organoborane catalysis to directly obtain aldol-type products. This new retrosynthetic disconnection method is compatible with enolisable coupling partners and achieves excellent chemoselectivity and substrate scope.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Kieran Nicholson, Yuxuan Peng, Natalia Llopis, Dominic R. Willcox, Gary S. Nichol, Thomas Langer, Alejandro Baeza, Stephen P. Thomas
Summary: This article presents a boron-catalyzed allylation of ketones with allenes, exploring the yield, regioselectivity, and diastereoselectivity of the reaction across functionalized substrates. Furthermore, the reaction is developed for asymmetric ketone allylation using an enantioenriched boron catalyst, achieving good yield, diastereoselectivity, and enantioselectivity. Mechanistic studies support a hydroboration-allylation-transborylation pathway.
Article
Chemistry, Organic
Lara Molla-Guerola, Alejandro Baeza
Summary: The synthesis of methyl 3,3-bis[4-(dimethylamino)phenyl]-2,2-dimethylpropanoate is achieved by alkylation of methyl isobutyrate silyl enol ether with bis[4-(dimethylamino)phenyl]methanol using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) as a solvent and reaction promoter. The reaction proceeds smoothly to produce the compound in good yield via a metal and additive-free procedure. The corresponding ester is fully characterized.
Article
Chemistry, Organic
Lara Molla-Guerola, Alejandro Baeza
Summary: The synthesis of (E)-2-(1,3-diphenylallyl)-3,5-dimethoxyphenol is achieved with high yield under a metal and additive-free procedure using 1,1,1,3,3,3-hexafluoroispropanol (HFIP) as a solvent and reaction promoter.
Article
Chemistry, Multidisciplinary
Manel Khiat, Fatima-Zohra Zradni, Souad Kasmi-Mir, Alejandro Baeza
Summary: An electrochemical study was conducted on merocyanines salts, which were transformed into TTTAF molecules, identified as pi-electron donor molecules. The structure of the newly synthesized molecules was confirmed using various analytical techniques.
INDONESIAN JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Applied
Paz Trillo, Alejandro Baeza
ADVANCED SYNTHESIS & CATALYSIS
(2017)
