Article
Chemistry, Organic
Matthew J. Mailloux, Gabrielle S. Fleming, Shruti S. Kumta, Aaron B. Beeler
Summary: A unified approach to azepines via dearomative photochemical rearrangement of aromatic N-ylides is described, yielding mono- and polycyclic azepines in high yields. This ring-expansion technique provides a new mode of access to functionalized azepines from N-heteroarenes with only two straightforward steps and simple starting materials.
Article
Chemistry, Organic
Zhiqiong Tang, Fang Zhang, Tengfei Yao, Xun-Shen Liu, Yuanyuan Liu, Lu Liu
Summary: This paper presents a dearomative iodocyclization of N-(o-alkynyl)aryl isoindole, which leads to the formation of various biologically active benzoindoleazine skeletons containing alkenyl iodine. The resulting products can undergo further cycloaddition or coupling reactions to form a series of highly functionalized N-fused polycyclic scaffolds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zhaojiang Shi, Wei-Zhen Wang, Nan Li, Yaofeng Yuan, Ke-Yin Ye
Summary: We have unraveled an electrochemical dearomative spirocyclization of N-acyl thiophene-2-sulfonamides, which incorporates various nucleophilic agents to afford remotely functionalized spirocyclic dihydrothiophenes. The novel spirocyclic scaffolds have shown promising antitumor activities, thanks to the highly regioselective 5-exo-trig spirocyclization.
Article
Chemistry, Organic
Jicheng Hou, Junhao Yin, Hao Han, Qirui Yang, Yougui Li, Yazhou Lou, Xiang Wu, Yang'en You
Summary: A highly regio- and stereoselective hydrochlorination/cyclization of enynes has been achieved using FeCl3 catalysis. This protocol utilizes acetic chloride as the chlorine source and H2O for protonation via a cationic pathway, resulting in Z isomers of heterocyclic alkenyl chloride compounds with high yields (<= 98%) and excellent regioselectivity.
Article
Chemistry, Organic
Emily P. Bacher, Kevin J. Koh, Antonio J. Lepore, Allen G. Oliver, Olaf Wiest, Brandon L. Ashfeld
Summary: A phosphorus(III)-mediated dearomatization of ortho-substituted dianiline squaraine dyes led to the formation of exotic benzofuranone and oxindole scaffolds with a linear side chain comprised of an enol, a phosphorus ylide, and 2,4-disubstituted aniline. Mechanistic evaluation revealed a significant dependence on the acidity of the aniline ortho substituent, with the rearrangement adducts reverting back to the parent squaraine in the presence of a Bronsted acid.
Article
Chemistry, Multidisciplinary
Yang Xiong, Johannes Grosskopf, Christian Jandl, Thorsten Bach
Summary: The photochemical synthesis of unknown 2-oxospiro[azetidine-3,3'-indolines], 2,4-dioxospiro[azetidine-3,3'-indolines], and 1-oxo-1,3-dihydrospiro[indene-2,3'-indolines] is described. The reaction involves dearomatization of the indole core via energy transfer and subsequent ring closure with diastereoselectivity. These spirocyclic products can be further functionalized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng Yang, Qiang Wang, Bing-Hui Cui, Xiao-Dong Zhang, Hang Liu, Yue-Yuan Zhang, Jia-Liang Liu, Wen-Yu Huang, Ren-Xiao Liang, Yi-Xia Jia
Summary: This study developed a cobalt-catalyzed enantioselective [3 + 2] annulation of N-heteroarenes with alkynes, providing a straightforward access to a variety of N-spiroheterocyclic molecules with excellent enantioselectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Huamin Wang, Huiling Shao, Ankita Das, Subhabrata Dutta, Hok Tsun Chan, Constantin Daniliuc, K. N. Houk, Frank Glorius
Summary: In this study, a photoinduced ring enlargement method of thiophenes was developed, which involves the insertion of bicyclo[1.1.0]butanes to form eight-membered bicyclic rings under mild conditions. The synthetic value, broad functional-group compatibility, and excellent chemo- and regioselectivity were demonstrated by scope evaluation and product derivatization. Experimental and computational studies suggested a photoredox-induced radical pathway.
Article
Chemistry, Organic
Lishuang Ma, Wenxu Feng, Yanyan Xi, Xuebo Chen, Xufeng Lin
Summary: In this study, accurate electronic structure calculations were performed to investigate the reaction mechanisms of the electron donor-acceptor complex in visible-light-mediated reactions. The results show the significance of noncovalent interactions in controlling the excitation energy levels and reaction competitiveness of the complex.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shao-Bo Duan, Hong-Yu Zhang, Yue Ma, Jiquan Zhao, Ya-Ping Han, Yuecheng Zhang, Yong -Min Liang
Summary: An elegant Pd-catalyzed method for the synthesis of structurally diverse indolines is reported in this paper. The method also exhibits good tolerance towards functional groups and shows synthetic robustness during scale-up experiments and product derivatization.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Qiumi Wang, Sicheng Li, Guosheng Yang, Xinyu Zou, Xi Yin, Juhua Feng, Huabao Chen, Chunping Yang, Li Zhang, Cuifen Lu, Guizhou Yue
Summary: The allylation of N-unsubstituted isatin N,N'-cyclic azomethine imines with Morita-Baylis-Hillman carbonates in the presence of 1-10 mol% DABCO in DCM at room temperature resulted in the rapid formation of N-allylated and N, beta-diallylated isatin N,N'-cyclic azomethine imine 1,3-dipoles in moderate to high yields. This reaction offers mild reaction conditions, practical operability, and short reaction times in most cases. Furthermore, the alkylated products can be transformed into novel bicyclic spiropyrrolidine oxoindole derivatives through [3+2] or [3+3]-cycloaddition reactions with maleimides or Knoevenagel adducts.
Article
Chemistry, Multidisciplinary
Tamanna Khandelia, Subhendu Ghosh, Bhisma K. Patel
Summary: A Cu(OTf)(2)-mediated regioselective dearomative aryl-hydroxylation across the C(sp(2))=N bond of 2-aryl quinoxalines and bis-Narylation of (benz)imidazoles were developed using aryl boronic acids. For the dearomative aryl-hydroxylation, the C-center should be electrophilic (ca. 0.08), the N-center nucleophilic (ca. -0.50), and the C(sp(2))=N bond polarized (delta e = 0.609).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yue Ma, Qing-Hui Liu, Ya-Ping Han
Summary: An elegant catalytic system has been developed for the assembly of optically active indoline scaffolds containing quaternary carbon centers at the C2 position. The system showed excellent yields, enantioselectivities, and diastereoselectivities through a tandem reaction that involved oxidative addition, carbon palladation, migratory insertion, and beta-elimination sequences. The practicality of the system was demonstrated through scaled-up experiments and late-stage derivatization, highlighting its potential applications in synthetic chemistry, medicinal chemistry, and material science.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Shiho Ishigaki, Yuki Nagashima, Daiki Yukimori, Jin Tanaka, Takashi Matsumoto, Kazunori Miyamoto, Masanobu Uchiyama, Ken Tanaka
Summary: The authors present a new protocol for the dearomative carbo-sila-boration of quinolines using organoboron and organosilicon compounds. This method has potential applications in materials science and medicinal chemistry.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Chao Zhou, Andrey Shatskiy, Azamat Z. Temerdashev, Markus D. Karkas, Peter Diner
Summary: The study demonstrates a dearomative annulation cascade through photoredox-mediated C-O bond activation of aromatic carboxylic acids to produce two types of spirocyclic frameworks. The protocol is further extended to challenging intermolecular tandem sequences, resulting in complex spirocyclic lactams.
COMMUNICATIONS CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Shanyu Tang, Guillaume Vincent
Summary: The oxidative coupling of tyrosine and tryptophan units plays a crucial role in the total synthesis of certain peptide-derived marine and terrestrial natural products such as diazonamides, azonazine, and tryptorubin A. This Minireview focuses on the biosynthesis and bioinspired synthesis of natural products with these structures, highlighting the challenges and innovative solutions adopted by synthetic chemists in their synthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Maxime Jarret, Hussein Abou-Hamdan, Cyrille Kouklovsky, Erwan Poupon, Laurent Evanno, Guillaume Vincent
Summary: Divergent oxidative couplings were developed between the indole nucleus and the C16-malonate, leading selectively to the formation of the N1-C16 bond of pleiocarpamine or the C7-C16 bond of strictamine. This approach allowed for the synthesis of the scaffold of talbotine.
Article
Chemistry, Multidisciplinary
Kangdong Mo, Xiaocong Zhou, Ju Wu, Yufen Zhao
Summary: A robust dearomative denitration method has been developed through a radical ipso-cyclization process, leading to the synthesis of valuable phosphonated or trifluoromethylated azaspiro[4.5]trienones with good functional group tolerance. This approach represents a convenient and powerful way to activate nitroarenes in a radical manner.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Nazarii Sabat, Weiping Zhou, Vincent Gandon, Xavier Guinchard, Guillaume Vincent
Summary: This study reports a method for the direct addition of arenes to the C3 position of unprotected indoles using triflic acid at room temperature. This simple and efficient method allows for the synthesis of biologically relevant 3-arylindolines and 3,3-spiroindolines in high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Shanyu Tang, Regis Guillot, Laurence Grimaud, Maxime R. Vitale, Guillaume Vincent
Summary: In this study, we report the direct carbamoylation or cyanation of benzylic C(sp3)-H bonds via an electrochemical process, leading to the formation of structures found in biologically relevant compounds and drugs. This transformation occurs under mild conditions without the need for external oxidants or prefunctionalized substrates.
Article
Chemistry, Organic
Kangdong Mo, Xiaocong Zhou, Ju Wu, Yufen Zhao
Summary: A robust and green electrochemical method was developed for the dearomatization of indoles, where a fluorine-containing group was merged with an indole nucleus under oxidant-free conditions, resulting in the synthesis of a diverse array of tri- and difluoromethylated 3,3-spiroindolines with good functional group tolerance.
Article
Chemistry, Multidisciplinary
Wei Cao, Yingchao Dou, Cyrille Kouklovsky, Guillaume Vincent
Summary: The first total synthesis of the monoterpene indole alkaloids ophiorrhine A is reported via a late stage bioinspired intramolecular Diels-Alder cycloaddition. The synthesis includes the construction of the indolopyridone moiety, cyclodehydration, and the desired spontaneous intramolecular Diels-Alder cycloaddition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Anais Rousseau, Guillaume Vincent, Cyrille Kouklovsky
Summary: A convergent strategy for the synthesis of leustroducsins and phoslactomycins has been designed, and the synthesis and coupling of three main fragments have been accomplished.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kangdong Mo, Xiaocong Zhou, Ju Wu, Yufen Zhao
Summary: An efficient and environmentally friendly electro-chemical method has been developed for the dearomatization of indoles. This method yielded a series of azido-containing spirocyclic indolines with good tolerance to functional groups. Cyclic voltammetry experiments supported the proposed mechanism involving the oxidation of Mn-II-N-3 species. Synthetic transformations offer an alternative approach for the synthesis of functionalized indolines.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Audrey Mauger, Maxime Jarret, Aurelien Tap, Remi Perrin, Regis Guillot, Cyrille Kouklovsky, Vincent Gandon, Guillaume Vincent
Summary: We synthesized highly strained pentacyclic caged framework of mavacuran alkaloids and successfully achieved the concise total synthesis of C-fluorocurine, C-profluorocurine, C-mavacurine, normavacurine, 16-epi-pleiocarpamine and taberdivarine H. A strategy involving late-stage Michael addition and intermolecular 1,4-addition reactions was designed. The first total syntheses of C-profluorocurine and C-fluorocurine were achieved through dihydroxylation of C-mavacurine and a pinacol rearrangement, respectively.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Kangdong Mo, Xiaocong Zhou, Jian Wang, Ju Wu, Yufen Zhao
Summary: A general and robust strategy for the synthesis of phosphonylatedspirocyclic indolines has been developed through Cp2Fe-catalyzed electrochemical dearomaztizaion of indoles, which has been proven challenging to achieve via chemical oxidants. A range of phosphonylated 3,3-spiroindolines were obtained in moderate to good yields with excellent diastereoselectivities. The synthetic application was further illustrated by its easy scalability and the antitumor activity of the product.
Article
Chemistry, Organic
Cyrille Kouklovsky, Erwan Poupon, Laurent Evanno, Guillaume Vincent
Summary: In this paper, we reported on our efforts towards the total synthesis of mavacuran alkaloids and their highly natural complex bis-indoles. Through a combination of bioinspired and non-bioinspired synthetic routes, we successfully synthesized several mavacuran alkaloids.
Review
Chemistry, Organic
Xiaocong Zhou, Ju Wu, Yufen Zhao
Summary: Functionalized oxindole derivatives are widely present in drugs and natural products. A green and efficient method for accessing these derivatives has been proven promising in drug discovery.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Shanyu Tang, Guillaume Vincent
Summary: We have developed a convergent paired electrolysis method for the arylative functionalization of a benzylic C(sp(3))-H bond. This process involves the coupling of a benzylic radical or carbocation with a 1,4-dicyanoarene radical anion to form the desired C-C bond. One of the challenges overcome was preventing the formation of overoxidized coupling products at the bisbenzylic position.
Review
Biochemistry & Molecular Biology
Audrey Mauger, Maxime Jarret, Cyrille Kouklovsky, Erwan Poupon, Laurent Evanno, Guillaume Vincent
Summary: This review provides a comprehensive coverage of mavacuranes alkaloids from early reports to the end of 2020, detailing their unique characteristics, skeleton, and synthetic pathways, with a focus on the core and bisindole assemblies.
NATURAL PRODUCT REPORTS
(2021)
