Article
Chemistry, Organic
Satish B. Thopate, Lakshmi Revati Magham, Shrabani Dinda, Rambabu Chegondi
Summary: This work presents the development of an unconventional and highly enantioselective solvent-promoted Rauhut-Currier cyclization of enal-tethered cyclohexadienone. The reaction involves the reactivity of a Jorgensen-Hayashi catalyst through the merging of iminium and enamine activation. The asymmetric desymmetrization reaction shows broad substrate scope with good yields and high to excellent enantioselectivity. DFT calculations suggest that the rate-limiting step is the elimination of the alkoxy group, which proceeds through proton abstraction by solvent instead of a direct 1,3-proton shift.
Article
Chemistry, Multidisciplinary
Anandarao Munakala, Mandalaparthi Phanindrudu, Rambabu Chegondi
Summary: The development of transition-metal catalyzed enantioselective and diastereoselective transformations has led to significant advances in synthetic organic chemistry, with a focus on the stereoselective desymmetrization of prochiral cyclohexadienones. In recent years, several research groups have made progress in this area, utilizing a variety of transition-metal catalysts to access highly functionalized and stereochemically enriched scaffolds.
Article
Chemistry, Multidisciplinary
Lakshmi Revati Magham, Satish B. Thopate, Abdus Samad, Rambabu Chegondi
Summary: This paper reports a method for the asymmetric desymmetrization of prochiral enal-tethered cyclohexadienones via C3-selective Friedel-Crafts alkylation, leading to the construction of complex molecules with multiple stereocentres. The reaction is triggered by the LUMO-lowering iminium activation and HOMO-raising enamine activation. The resulting bicyclic enones can undergo acid-mediated intramolecular annulation from the C2-position, yielding highly strained cyclohepta[b]indoles with excellent enantioselectivity and diastereoselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Corinne Coutant, Paul De Bonfils, Pierrick Nun, Vincent Coeffard
Summary: The advent of asymmetric organocatalysis has revolutionized the way chemists create or break chemical bonds, enabling new strategies for enantioselective functionalization. This success is attributed to various activation modes and the availability of numerous chiral organic catalysts. Selective functionalization of compounds with multiple activation sites, such as cyclohexanone-derived dienones, has also contributed to breakthroughs in this field. These compounds can undergo diverse transformations and offer new opportunities for natural product synthesis. This review focuses on intermolecular functionalization of (cross)-conjugated cyclohexanone-derived compounds using asymmetric organocatalysis.
Article
Chemistry, Multidisciplinary
Soumen Barik, Sayan Shee, Soumik Das, Rajesh G. Gonnade, Garima Jindal, Subrata Mukherjee, Akkattu T. Biju
Summary: This study describes the atroposelective synthesis of N-aryl succinimides with axially chiral C-N bonds catalyzed by N-heterocyclic carbenes, achieving good yields and ee values. Preliminary investigations were also conducted on the rotation barrier for the C-N bond, temperature dependence, and detailed DFT studies on the mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Min Zhu, Martin Oestreich
Summary: A group-selective monosilylation of silanediols using List's counteranion-directed silylation methodology is described. The enantioselectivity is achieved by generating a silylium-ion-like silicon electrophile from an allylic silane paired with an imidodiphosphorimidate (IDPi), enabling discrimination of the two hydroxy groups attached to the prochiral silicon atom. Furthermore, the enantioselectivity is improved by a subsequent kinetic resolution, resulting in silicon-stereogenic disiloxanes with high enantiocontrol.
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Editorial Material
Chemistry, Physical
Svetlana B. Tsogoeva, Guangbin Dong, Lutz Ackermann
Summary: This Special Collection discusses the latest strategies and progress in ring synthesis, including catalytic domino reactions and one-pot processes. Contributions cover transition-metal catalysis, organocatalysis, nanocatalysis, and photoredox catalysis for preparing carbocyclic and heterocyclic compounds.
Review
Chemistry, Multidisciplinary
Lu Yang, Bingren Wang, Xianjie Yin, Qingle Zen
Summary: Sulfenate anions as key intermediates in enantioselective synthesis have attracted attention in recent years. Developing new synthetic methods to generate sulfenate anions allows for the preparation of various enantiopure sulfoxides, which are widely used as auxiliaries, ligands, organocatalysts, and biologically active compounds. This review covers the in situ preparation methods and recent applications of sulfenate anions in catalytic asymmetric synthesis of chiral sulfoxides.
Review
Chemistry, Physical
Nilanjana Majumdar
Summary: Catalytic asymmetric transformation is a powerful strategy for synthesizing diverse nonracemic molecular entities. Carboxylic acids have been explored as building blocks in this area, and significant advancements have been made in the last three decades. They can act as both C- and O-nucleophiles, as well as electrophiles, in asymmetric reactions under catalytic conditions.
Article
Chemistry, Organic
Daniel Lowicki, Justyna Watral, Maciej Jelecki, Wiktor Bohusz, Marcin Kwit
Summary: An efficient enantioselective protonation of 2-methyl-1-tetralone lithium enolate catalyzed by salan-type diamines is reported in this study. A broad series of salan-type catalysts were synthesized and tested in the reaction, with a chiral amine organocatalyst showing better results than a stoichiometric protonating agent for the first time. The use of only 10 mol% of salan allows for high yield and enantiomeric excess up to 75% in obtaining the title ketone.
Review
Chemistry, Applied
Sara Meninno, Francesca Franco, Maurizio Benaglia, Alessandra Lattanzi
Summary: Pyrazoleamides have gained attention as reactive and practical surrogates in asymmetric catalysis, particularly in a variety of metal- and organocatalytic transformations. Their relevance has extended to photoredox catalysis and challenging stereoselective bond-forming reactions in recent years.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Organic
Carmen Najera, Francisco Foubelo, Jose M. Sansano, Miguel Yus
Summary: This review summarizes the recent advancements in enantioselective desymmetrization reactions using metal-catalyzed, organocatalyzed, and enzymatic processes. These asymmetric strategies have been successfully applied to a wide range of organic compounds, including diarylalkanes, silanes, alcohols, amines, and unsaturated compounds. The classical desymmetrization of various compounds by acylation, alkylation, and oxidation methods are important processes in organic synthesis. Desymmetrization methodologies have also been applied to small ring carbocycles and heterocyclic systems. The synthetic applications of these strategies in the total synthesis of natural products and biologically active compounds are highlighted.
Article
Chemistry, Organic
Ashok Donthoju, Anandarao Munakala, Sushma Ellandula, Rambabu Chegondi
Summary: In this study, we have reported a palladium(0)-catalyzed decarboxylative oxa-Michael addition/remote alpha-allylation/1,3-migration reaction with high yields. The reaction is triggered by a base-mediated retro-Michael ring-opening reaction and subsequent syn-selective oxa-Michael addition.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Physical
Xue-Xin Zhang, Ying Zhang, Ling Liao, Yang Gao, Heng E. M. Su, Jin-Sheng Yu
Summary: This minireview summarizes the recent advancements in catalytic enantioselective isomerization and tandem reactions, discusses their advantages and limitations, and highlights the synthetic opportunities for further development.
Article
Chemistry, Multidisciplinary
Andrew M. Harned
CHEMICAL COMMUNICATIONS
(2015)
Article
Chemistry, Organic
Robert A. Craig, Steven A. Loskot, Justin T. Mohr, Douglas C. Behenna, Andrew M. Harned, Brian M. Stoltz
Article
Chemistry, Organic
Nicholas G. Moon, Andrew M. Harned
Article
Chemistry, Organic
Nicholas G. Moon, Andrew M. Harned
ORGANIC & BIOMOLECULAR CHEMISTRY
(2017)
Article
Chemistry, Multidisciplinary
Rakesh G. Thorat, Andrew M. Harned
CHEMICAL COMMUNICATIONS
(2018)
Article
Chemistry, Organic
Andrew M. Harned
ORGANIC & BIOMOLECULAR CHEMISTRY
(2018)
Article
Chemistry, Organic
Andrew M. Harned
Article
Multidisciplinary Sciences
Nicholas G. Moon, Andrew M. Harned
ROYAL SOCIETY OPEN SCIENCE
(2018)
Article
Chemistry, Multidisciplinary
Kelly A. Volp, Andrew M. Harned
CHEMICAL COMMUNICATIONS
(2013)
Article
Chemistry, Organic
Ting Tang, Andrew M. Harned
ORGANIC & BIOMOLECULAR CHEMISTRY
(2018)
Article
Chemistry, Organic
Andrew M. Harned
TETRAHEDRON LETTERS
(2014)
Article
Chemistry, Organic
Rakesh G. Thorat, Bailey A. Brooks, Brandon Nichols, Andrew M. Harned
Article
Chemistry, Organic
Andrew M. Harned, Brian M. Stoltz
Article
Chemistry, Multidisciplinary
Ting Tang, Nicholas G. Moon, Lydia McKay, Andrew M. Harned
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.
