Article
Chemistry, Multidisciplinary
Ramesh Kotipalli, Undamatla Suri Babu, Jagadeesh Babu Nanubolu, Maddi Sridhar Reddy
Summary: Here, we report a novel selective annulation reaction using a Rh-catalyst, which allows the synthesis of pyranoindole cyclic motifs by reacting indolyl oxopropanenitrile with hydroxy-alkynoates. The reaction takes advantage of the unique reactivity of enol oxygen, resulting in regio- and stereoselective assembly of the desired compounds through a five-membered oxy-rodacycle formed via C-H activation guided by enolic- and propargyloxy dual coordination.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Heyin Li, Mengjun Huang, Zhenlei Zou, Zhen Wang, Yifan Li, Chao Sun, Wangzhe Chen, Yi Pan, Weigang Zhang, Yi Wang
Summary: Sulfur(vi) fluoride exchange (SuFEx) chemistry is a next-generation click reaction with high reactivity and stability. Bifunctional handles containing the fluorosulfonyl group have synthetic value for drug discovery. However, the direct photoredox-catalyzed fluorosulfonyl-borylation process has not been explored due to system incompatibility and limited synthetic strategies. This study developed a sequential photocatalytic radical difunctionalization strategy for the synthesis of vicinal fluorosulfonyl borides (VFSBs) with great potential in skeleton linkage and drug modification.
Article
Chemistry, Organic
Jinghui Hu, Qiang Du, Yao Zhao, Fei Zhang, Rizhi Chen, Jianrong Steve Zhou, Xiaojin Wu
Summary: A nickel-catalyzed intermolecular arylcyanation reaction of 8-aminoquinolinyl beta,gamma-unsaturated amides is reported. Diverse beta-cyano gamma-aryl amides with exclusive chemo- and regioselectivity were directly obtained through a three-component reaction. The practicality of this approach was further demonstrated through multigram scale reactions, expanded transformations of the nitrile product, late-stage modification of complex molecules, and direct drug synthesis.
Article
Chemistry, Organic
Kundo Kim, Subin Park, Yunmi Lee
Summary: This study describes a highly efficient and regioselective KOt-Bu-catalyzed addition reaction of substituted indoles to terminal or disubstituted allylic sulfones, allowing for the synthesis of versatile sulfonyl-substituted indoles and azoles with complete regioselectivity in good to excellent yields.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Huijun Qian, Hieu D. Nguyen, Leiyang Lv, Shuming Chen, Zhiping Li
Summary: The study developed an efficient method to incorporate the hydrazone moiety into the products through palladium/NHC-catalyzed fluoroallylation/annulation of gem-difluorocyclopropanes (gem-F(2)CPs) with hydrazones. Thermodynamically unstable fluorinated E-allylation products were obtained with aryl ketone hydrazones, while monofluorinated products with branched selectivity were obtained with di-alkyl ketone hydrazones. Two kinds of pyrazoles were obtained via a defluorinative allylation/annulation cascade with aldehyde hydrazones, and different carbon atoms of gem-F(2)CPs could be incorporated into the pyrazole rings regiospecifically. DFT calculations revealed that the divergent selectivity was kinetically controlled and the final C-C bond formation proceeded through a 7-membered TS.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Julia Burykina, Andrey D. Kobelev, Nikita S. Shlapakov, Alexander Yu Kostyukovich, Artem N. Fakhrutdinov, Burkhard Koenig, Valentine P. Ananikov
Summary: The first example of an intermolecular thiol-yne-ene coupling reaction is reported, which enables the one-pot construction of C-S and C-C bonds. Thiol-yne-ene coupling reaction opens up new possibilities for building complex molecules and accessing highly functionalized products. The unique photoredox cycle involved in this reaction was revealed through various experimental techniques and computational modeling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Liye Chen, Katerina G. Malollari, Adam Uliana, John F. Hartwig
Summary: The lack of functional groups in polyolefins limits their applications, but the functionalization of C-H bonds holds promise for incorporating functionalities into ethylene and linear alpha-olefins polymers. The selective functionalization of polyolefins derived from branched alkenes has not been achieved due to steric effects, but a polyfluorinated ruthenium-porphyrin catalyst successfully incorporates ketone units into polyisobutene without chain cleavage, resulting in a thermally stable polymer with enhanced wetting properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Feng Zhong, Zhi-Zhou Pan, Si-Wei Zhou, Hai-Jun Zhang, Liang Yin
Summary: The study demonstrates a regioselective asymmetric allylation of ketones using commercially available 1,4-pentadiene as a pronucleophile. Chiral tertiary alcohols with a terminal (Z)-1,3-diene unit are produced with high (Z)/(E) ratio and enantioselectivity. The partial isomerization of (E)-allylcopper(I) species to (Z)-allylcopper(I) species is observed during the reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Gang Liu, Congcong Yin, Xuanliang Yang, Anqi Li, Minyan Wang, Xumu Zhang, Xiu-Qin Dong
Summary: A highly chemo- and enantioselective hydrogenation method for beta-sulfonyl-alpha,beta-unsaturated ketones was successfully developed, producing a variety of enantioenriched gamma-ketosulfones in good to high yields with excellent selectivities. Gram-scale asymmetric hydrogenation was carried out smoothly with high yields and selectivities. Preliminary DFT computations provided a reasonable explanation for the observed high chemoselectivity and enantioselectivity.
Review
Chemistry, Physical
Vaezeh Fathi Vavsari, Mehri Seyed Hashtroudi, Saeed Balalaie
Summary: Ruthenium complexes are excellent catalysts for C-H activation and organic transformations. Combining Ru-catalyst with oxidants and additives in a one-pot process is a sustainable approach, reducing reaction steps and minimizing solvent usage during synthesis, work-up, isolation, and purification. This review focuses on the ruthenium-catalyzed organic transformations in a one-pot manner to synthesize heterocyclic backbones, including indoles, benzofurans, indazoles, pyrans, pyrimidines, quinolines, and isoquinolines.
Article
Chemistry, Physical
Guoqi Zhang, Haisu Zeng, Shengping Zheng, Michelle C. Neary, Pavel A. Dub
Summary: Molecular complexes of vanadium were found to catalyze the anti-Markovnikov hydroboration reaction of alkynes, generating vinyl boronate esters with high turnover numbers and tolerance towards various functional groups. Preliminary computational analysis of the catalytic cycle revealed complex reactivity and activity of the redox-active ligand.
Article
Chemistry, Physical
Pu-Fan Qian, Tao Zhou, Jun-Yi Li, Yi-Bo Zhou, Bing-Feng Shi
Summary: Chiral benzothiadiazine-1-oxides are sulfur-stereogenic compounds with structural diversity that have gained significant attention in drug discovery. This study reports the synthesis of these chiral molecules through an asymmetric [4 + 3] annulation reaction of sulfoximines with alpha,beta-unsaturated ketones, catalyzed by an achiral Ru(II) complex and assisted by a chiral carboxylic acid (CCA). The method allows for the preparation of a wide range of chiral benzothiadiazepine-1-oxides with various functional groups in high yields and excellent enantioselectivity, expanding the chemical space of chiral sulfoximines. Importantly, the oxidative cleavage of the products yields chiral N-benzoyl sulfoximines with a C-S chiral axis.
Article
Chemistry, Organic
Suresh Kumar Yadav, Balu Ramesh, Masilamani Jeganmohan
Summary: This study describes an air-stable, highly abundant, and cost-effective Co(III)-catalyzed redox-neutral [4 + 2] annulation reaction of aromatic sulfoxonium ylides with 1,3-diynes, resulting in the synthesis of useful substituted 1-naphthol derivatives in a regioselective manner. Furthermore, the prepared 1-naphthols with internal alkynes were converted into polycarbocyclic molecules and spiro-dienone derivatives with high yields. A possible reaction mechanism involving ortho C-H activation as a key step was proposed and supported by deuterium labeling and kinetic isotope labeling studies.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jiaoyu Wu, Lu Bai, Lingbo Han, Jingjing Liu, Xinjun Luan
Summary: A chemo- and regioselective Pd(0)-catalyzed spiroannulation method was successfully developed, utilizing readily available 1,2-dihaloarenes, alkynes, and 2-naphthols for rapid assembly of spirocarbocyclic molecules. The mechanistic studies revealed that the reaction proceeded through a cascade of oxidative addition, alkyne migratory insertion, and 2-naphthol-facilitated dearomatizing [4+1] spiroannulation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Lin Zhu, Dian Song, Yi-Han Liu, Meng-Di Chen, Xin-Ru Zhang, Meng-Yan You, Jun-Long Zhan
Summary: In this study, an Fe-catalyzed unprotected hydroxylamine mediated Heck-type coupling was developed for the regioselective synthesis of (E)-vinyl sulfones. Mechanism studies revealed the involvement of a radical process and the multiple roles of hydroxylamines as a mild oxidant and an in situ base. This transformation not only realizes C-S bond construction promoted by unprotected hydroxylamines, but also provides a practical and complementary method for the preparation of structurally important (E)-vinyl sulfones.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Thurpu Raghavender Reddy, Dodla Sivanageswara Rao, Kalvacherla Babachary, Sudhir Kashyap
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2016)
Article
Chemistry, Organic
Govindareddy Kundoor, Dodla Sivanageswara Rao, Sudhir Kashyap
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2016)
Article
Chemistry, Organic
Dodla S. Rao, Thurpu R. Reddy, Kalvacherla Babachary, Sudhir Kashyap
ORGANIC & BIOMOLECULAR CHEMISTRY
(2016)
Article
Chemistry, Organic
Suresh Kumar Battina, Sudhir Kashyap
TETRAHEDRON LETTERS
(2016)
Article
Chemistry, Organic
Dodla S. Rao, Thurpu R. Reddy, Sudhir Kashyap
ORGANIC & BIOMOLECULAR CHEMISTRY
(2018)
Article
Chemistry, Organic
Dodla S. Rao, Thurpu R. Reddy, Aakanksha Gurawa, Manoj Kumar, Sudhir Kashyap
Article
Chemistry, Organic
Manoj Kumar, Aakanksha Gurawa, Nitin Kumar, Sudhir Kashyap
Summary: A direct and highly stereoselective glycosylation reaction catalyzed by Bi(OTf)(3) has been reported. The chemoselectivity of deactivated glycal donors can be controlled by tuning the solvent, leading to improved substrate scope. The versatility of this method has been demonstrated in the synthesis of oligosaccharides, as well as the 2-deoxyglycosylation of high-value natural products and drugs.
Article
Chemistry, Multidisciplinary
Aakanksha Gurawa, Manoj Kumar, Sudhir Kashyap
Summary: The study reports a new photolytic radical-induced vicinal azidooxygenation reaction method, which can efficiently convert various functionalized substrates, including unactivated alkenes, and form high-value drug analogs and bioactive skeletons in late-stage transformations.
Article
Chemistry, Multidisciplinary
Manoj Kumar, Nitin Kumar, Aakanksha Gurawa, Sudhir Kashyap
Summary: An alternative and highly efficient method for L-rhamnosylation using ruthenium reagent as a dual catalyst has been developed. This method allows the synthesis of biologically active α-L-rhamnopyranosides in good yields and can tolerate diverse functional groups.
Article
Biochemistry & Molecular Biology
Manoj Kumar, Nitin Kumar, Aakanksha Gurawa, Sudhir Kashyap
Summary: We report a convenient and highly stereocontrolled approach for the synthesis of rare and vital D-talo and D-gulo sugars directly from economical D-galactal. This method, involving dual ruthenium-catalysis, achieves stereo-divergent synthesis through judicious selection of stereoelectronically diverse protecting groups. The synthetic utility of this approach has been demonstrated for the efficient assembly of D-talose and D-gulose sugars in natural products and bioactive scaffolds.
CARBOHYDRATE RESEARCH
(2023)
Article
Chemistry, Organic
Aakanksha Gurawa, Nitin Kumar, Sudhir Kashyap
Summary: This article presents a photo-induced method for the synthesis of vinyl sulfones and sulfonates, using sulfonium iodate species. The reaction shows high regioselectivity and substrate tolerance, making it an efficient and atom-economical synthetic approach.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Aakanksha Gurawa, Manoj Kumar, Sudhir Kashyap
Summary: The developed protocol allows for selective deprotection of acetyl groups in a wide range of substrates, including carbohydrates, amino acids, natural products, heterocycles, and general scaffolds. The environmentally friendly reagent system used in this method enables clean transformations under ambient conditions.
Article
Chemistry, Multidisciplinary
Aakanksha Gurawa, Manoj Kumar, Dodla S. Rao, Sudhir Kashyap
NEW JOURNAL OF CHEMISTRY
(2020)
Article
Chemistry, Organic
Manoj Kumar, Thurpu Raghavender Reddy, Aakanksha Gurawa, Sudhir Kashyap
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Thurpu Raghavender Reddy, Dodla Sivanageswara Rao, Sudhir Kashyap
CHEMICAL COMMUNICATIONS
(2019)
