Article
Chemistry, Organic
Santanu Mondal, Ravindra D. Aher, Venkati Bethi, Yu-Ju Lin, Tohru Taniguchi, Kenji Monde, Fujie Tanaka
Summary: This study reports amine-based catalyst systems for the enantioselective Mannich reactions of pyruvates as nucleophiles. The reactions of pyruvates and cyclic sulfonylimines yielded the desired Mannich products, including those with tetrasubstituted carbon centers, in high yields and enantioselectivities. The choice of acid in the amine-based catalyst system played a key role in the formation of Mannich products with high enantioselectivities.
Article
Chemistry, Multidisciplinary
Masamichi Yasui, Kengo Hanaya, Takeshi Sugai, Shuhei Higashibayashi
Summary: The metal-free thermal organocatalytic pinacol coupling of arylaldehydes has been developed, leading to the synthesis of various 1,2-diols. The reaction showed good tolerance towards different functional groups.
Review
Chemistry, Multidisciplinary
Yin Xu, Tong-Yi Zhai, Zhou Xu, Long-Wu Ye
Summary: Desymmetrization is a practical and efficient strategy in synthetic chemistry for assembling valuable molecular complexity. Organocatalysis has become a powerful tool in asymmetric catalysis, and recent progress has been made in combining organocatalysis with desymmetrization.
TRENDS IN CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Yan-Long Zheng, Stephen G. Newman
Summary: This article discusses two common families of chemical reactions - cross-coupling reactions and pi bond addition reactions - and the significant overlap between them. Recent advancements in catalysis have revealed the role of compounds such as esters, aldehydes, and alcohols in nickel- and palladium-catalyzed reactions, offering promising alternatives for the preparation of amides, ketones, substituted alcohols, alkanes, and more. The focus is on the key mechanistic steps that allow these non-traditional substrates to be incorporated into cross-coupling-like catalytic cycles.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ingolf Harden, Frank Neese, Giovanni Bistoni
Summary: The formation of Bronsted acid aggregates in asymmetric organocatalytic reactions has a significant impact on the stereo-controlling factors of the transformations. This study uses high-level quantum mechanical calculations to investigate the influence of catalyst structure and reaction conditions on the spontaneity of the aggregation process, shedding light on its importance.
Article
Chemistry, Multidisciplinary
Chuan-Wen Lei, Bo-Shuai Mu, Feng Zhou, Jin-Sheng Yu, Ying Zhou, Jian Zhou
Summary: The chemistry of carbocations has witnessed significant advances over the past 120 years, with current research focused on developing catalytic asymmetric reactions to overcome the intrinsic instability and high reactivity of prochiral carbocationic intermediates. Highly enantioselective protocols evolving prochiral carbocationic intermediates have been achieved through various strategies.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ingolf Harden, Frank Neese, Giovanni Bistoni
Summary: This study investigates the aggregation process of chiral organocatalysts derived from phosphoric acids using high-level quantum mechanical calculations. The results show that the formation of catalyst dimers is possible and the aggregation process can significantly affect the stereo-controlling factors, reaction kinetics, and selectivity of the transformations.
Article
Chemistry, Organic
Chen-Jun Peng, Jun-Ping Pei, Ying-Han Chen, Zhi-Yong Wu, Ming Liu, Yan-Kai Liu
Summary: An organocatalytic enantioselective conjugate addition-initiated reaction sequence of 2-hydroxycinnamaldehydes with various functionalized nitroalkanes has been described. The combination of iminium catalysis and thiourea hydrogen-bonding catalysis was found to be crucial for this enantioselective conversion, leading to the formation of diverse chiral chromanes embedded within a dioxa[3.3.1] or oxa[4.3.1] methylene-bridged ring system with high enantiomeric purity. The developed protocol shows great promise for the construction of various functionalities with complete diastereoselectivity due to the properties of the nitro group.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Organic
Paru Jamwal, Himani Vaid, Gunda Ananda Rao, Ramani Gurubrahamam, Kwunmin Chen
Summary: This review explores the asymmetric organocatalytic reactions of various electron-deficient racemic allenes with nucleophiles and electrophiles. It presents the literature on enantioselective functionalization of allenes using chiral phosphine, amine, phase transfer, bifunctional, and Bronsted acid catalysts, along with their mechanisms. The review also highlights the methods of obtaining enantioenriched allenes from racemic allenes through organocatalytic (dynamic) kinetic resolution techniques. Furthermore, it narrates the synthetic utility of these methodologies in the synthesis of target-oriented biologically active molecules.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Biochemistry & Molecular Biology
Leon Hoppmann, Olga Garcia Mancheno
Summary: The review focuses on the organocatalytic applications of silyl-dienolates in asymmetric vinylogous C-C bond formations, highlighting their high regioselectivities and catalytic characteristics.
Article
Chemistry, Organic
Lukas Hoff, Simon D. Schnell, Andrea Tomio, Anthony Linden, Karl Gademann
Summary: A silver-mediated Pd-catalyzed cross-coupling method for 3-bromo-1,2,4,5-tetrazine with boronic acids was presented in this study. It was found that electronic modification of the dppf ligand played a crucial role in achieving good turnover. Using this fast method, a variety of alkyl-, heteroatom-, and halide-substituted aryl- and heteroaryl-tetrazines were successfully prepared, with yields up to 87%.
Article
Chemistry, Multidisciplinary
Zhaofeng Gao, Jingwen Liu, Haizhou Huang, Huiling Geng, Mingxin Chang
Summary: The research reports on efforts to merge two asymmetric reductive amination reactions into a single-step transformation, utilizing specific catalyst and acid additives to successfully synthesize enantiopure secondary amine products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Pawel Huninik, Jakub Szyling, Agnieszka Czapik, Jedrzej Walkowiak
Summary: An efficient and simple method for the regioselective hydroboration of alkenes has been developed using pinacolborane and 1-ethyl-methylpyrrolidinium triflate as the reducing reagent and organocatalyst respectively. The protocol is scalable and compatible with various alkenes, providing moderate-to-excellent yields of organoboron compounds. The obtained alkylboronates can be further used in various transformations, and a reaction mechanism has been proposed based on literature and NMR studies.
Article
Chemistry, Organic
Patricia Cmelova, Peter Sramel, Barbora Zahradnikova, Viktoria Modrocka, Henrich Szabados, Maria Meciarova, Radovan Sebesta
Summary: This paper presents the synthesis and evaluation of a bifunctional organic catalyst that can efficiently catalyze the selective synthesis of polyfunctional molecules. The hybrid organocatalysts consist of Pro-Pro dipeptide and thiourea moiety connected via a 1,2-diaminocyclohexane unit.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shiqi Jia, Yu Chang, Yuhong Tian, Hui Mao, Wenling Qin, Pengfei Wang, Hailong Yan
Summary: An organocatalytic approach using VQM intermediates was employed to introduce various alcohols into the carbonyl of alpha,beta-unsaturated ketones, followed by dearomatization to yield stereo-defined cyclic ethers via a cascade process. This strategy provides efficient access to the unexplored chiral cyclic ether chemospace.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Laura K. G. Ackerman, Jesus I. Martinez Alvarado, Abigail G. Doyle
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Organic
Jesus I. Martinez Alvarado, Alyssa B. Ertel, Andrea Stegner, Erin E. Stache, Abigail G. Doyle
Article
Multidisciplinary Sciences
Benjamin J. Shields, Jason Stevens, Jun Li, Marvin Parasram, Farhan Damani, Jesus I. Martinez Alvarado, Jacob M. Janey, Ryan P. Adams, Abigail G. Doyle
Summary: Reaction optimization and parameter optimization are crucial in synthetic chemistry and artificial intelligence, respectively. Bayesian optimization algorithm has shown exceptional performance in tuning machine learning models and has been applied in chemistry. However, its application in reaction optimization in synthetic chemistry has not been explored. Adopting Bayesian optimization methods into everyday laboratory practices could lead to more efficient synthesis of functional chemicals.
Review
Chemistry, Multidisciplinary
Andrzej M. Zuranski, Jesus I. Martinez Alvarado, Benjamin J. Shields, Abigail G. Doyle
Summary: The article introduces the application of machine learning in the field of chemistry, predicting chemical reaction yields by building supervised machine learning models. The study finds that using DFT-based featurization can significantly improve out-of-sample prediction performance, supporting the formulation of mechanistic hypotheses. Further research and development are needed to establish machine learning as a key tool in reaction modeling.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Paul T. Cesana, Beryl X. Li, Samuel G. Shepard, Stephen Ting, Stephanie M. Hart, Courtney M. Olson, Jesus I. Martinez Alvarado, Minjung Son, Talia J. Steiman, Felix N. Castellano, Abigail G. Doyle, David W. C. MacMillan, Gabriela S. Schlau-Cohen
Summary: By mimicking the modular structure of photosynthesis, attaching R-phycoerythrin to a transition metal photocatalyst has increased the efficiency of the biohybrid photocatalyst. Experimental results demonstrate a significant increase in yields for reactions at red wavelengths using the biohybrid photocatalyst.
Review
Chemistry, Multidisciplinary
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes, Jesus I. Martinez Alvarado, Song Lin
Summary: Frustrated radical pairs (FRPs) are able to coexist in solution due to steric repulsion or weak bonding association between two distinct radicals, which would otherwise annihilate each other. They are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors and exhibit orthogonal chemical properties. FRPs have been found to be capable of homolytically activating various chemical bonds and are being extensively explored in synthetic organic chemistry, including C-H bond functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
