Review
Biochemistry & Molecular Biology
Olga Bakulina, Anna Inyutina, Dmitry Dar'in, Mikhail Krasavin
Summary: This review summarizes recent developments in multicomponent reactions of diazo compounds, analyzing the role of diazo reagents and the type of interaction between components. In contrast to previous reviews mostly focused on metal catalyzed transformations, this work covers a substantial amount of organocatalytic or catalyst-free methodologies.
Article
Chemistry, Organic
Hong Zhang, Jieyin He, Wendi Xu, Liangliang Yang, Xue Zhang, Haiyang Wang, Ming Lang, Jian Wang, Shiyong Peng
Summary: A copper-catalyzed cascade reaction between 1,6-enynes and sulfoxonium ylides, leading to the formation of structurally intriguing 2,3-disubstituted indolines, has been reported. The reaction exhibited moderate to excellent yields and good chemo-, regio-, and diastereoselectivities under mild reaction conditions. Notably, the reactivity of sulfoxoniumylide-derived copper-carbene was found to be different from that of diazo copper-carbene. The proposed mechanism involves the formation of an initial ammonium ylide rather than an allene.
Article
Chemistry, Multidisciplinary
Justus Reitz, Patrick W. Antoni, Julian J. Holstein, Max M. Hansmann
Summary: Recently, stable diazoalkenes have gained attention in organic chemistry as a new substance class. A general synthetic approach using a Regitz-type diazo transfer with azides is established, which allows for the synthesis of pyridine diazoalkenes. This approach is applicable to weakly polarized olefins as well. The properties of these pyridine-derived diazoalkenes are distinct from previously reported classes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Matthieu J. R. Richter, Frederic J. Zecri, Karin Briner, Stuart L. Schreiber
Summary: In this study, a novel and efficient synthesis method for cyclopropane-fused lactams was developed using specific chemical agents. The method demonstrated broad applicability and modularity, allowing for the synthesis of structurally diverse complex molecular scaffolds. The utility of this method was further highlighted through the concise synthesis of two therapeutic agents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Li-Jun Wu, Qianru Wang, Jianping Guo, Junnian Wei, Ping Chen, Zhenfeng Xi
Summary: Through the synergy of heterogeneous and homogeneous synthetic approaches, N-containing organic compounds can be synthesized using activated N-containing species prepared from N-2 gas and suitable carbon sources. Li2CN2 was successfully prepared as the activated N-containing species and utilized as a novel synthetic synthon for constructing N-containing organic compounds. Various valuable nitrogen-containing compounds were synthesized in moderate to excellent yields using Li2CN2 under mild conditions, including N-15-labeled products with anti-cancer activity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shengjie Jiang, Yanping Cai, Thayalan Rajeshkumar, Iker del Rosal, Laurent Maron, Xin Xu
Summary: This work presents the synthesis, characterization, and reactivity of the first well-defined zinc α-diazoalkyl complex. The complex reacts with a nickel catalyst to form an α-zincated phosphorus ylide, or undergoes [3+2] cycloaddition with CO2 or CO to produce a five-membered heterocyclic product. The use of CO in the cycloaddition reaction is unprecedented, demonstrating a novel CO reaction mode.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Cheng Zhang, Kemiao Hong, Shanliang Dong, Mengting Liu, Matthias Rudolph, Martin C. Dietl, Jian Yin, A. Stephen K. Hashmi, Xinfang Xu
Summary: The exploration of intermediates for selective cycloadditions in the synthesis of fused and bridged-ring systems is of great interest. A concise strategy for the catalytic generation of cyclic dienyl gold carbene species via a gold-promoted diazo-enyne carbocyclization process is presented. The resulting carbene intermediates undergo cycloadditions with different dipolarophiles, leading to a diverse array of fused and bridged skeletons with high selectivity. This method provides a tool for accessing ring systems with complexity and diversity, complementing existing protocols relying on open-chained vinylcarbene species.
Article
Chemistry, Multidisciplinary
Sudeshna Mondal, Chandan Kumar Giri, Mahiuddin Baidya
Summary: The weakly coordinating enaminone functionality is essential for the ruthenium-catalyzed C-H bond activation strategy, enabling the regioselective coupling of arenes with diazonaphthoquinones to produce polycyclic benzocoumarins in high yields. The protocol operates through a Ru(II)/Ru(IV) catalytic pathway and allows for the diversification of various pharmacophore-coupled substrates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yangjinxiu Zhou, Tengfei Pang, Yu Liu, Fangrui Zhong, Guojiao Wu
Summary: We present a highly intriguing and underexplored multi-component reaction involving diazo molecules for polyene formation. This reaction involves coupling of 2,2,2-trifluorodiazoethane and aryl alkynes mediated by iodine under visible light. The reaction provides a straightforward and step-economic access to bistrifluoromethylated 1,3,5-trienes in high stereoselectivity by creating three C=C bonds in a single step under mild conditions.
Article
Chemistry, Multidisciplinary
Mathilde Rigoulet, David Vesseur, Karinne Miqueu, Didier Bourissou
Summary: This study reveals that Aryl trifluoromethyl diazomethanes can be decomposed to form alpha-CF3 substituted carbene complexes under the effect of certain gold(I) complexes. The bonding situation of these complexes is thoroughly evaluated, showing the influence of the aryl substituent and Au in stabilizing the electrophilic carbene center. Reactivity studies confirm the typical carbene-type behavior for one of the complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yu-Ting Tian, Fa-Guang Zhang, Jun-An Ma
Summary: A novel Et3N-catalyzed [3 + 2] cycloaddition reaction has been developed for the synthesis of various pyrazoles from allenoates by reacting with acceptor diazo compounds. 3-Alkynoates can also participate in the reaction by isomerizing to allenoates in situ.
Article
Chemistry, Multidisciplinary
Ziyan Zhang, Nikita Kvasovs, Anastasiia Dubrovina, Vladimir Gevorgyan
Summary: This method utilizes visible light-induced and Bronsted acid-assisted generation of hybrid palladium C(sp(3))-centered radical intermediate, enabling efficient transformation of a wide range of vinyl arenes, heteroarenes, and diazo compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Manqing Wang, Qianting Zhou, Xinying Zhang, Xuesen Fan
Summary: A condition-controlled divergent synthesis of imidazoindolone spiro-isoquinolinones (IISIQs) was presented, which involved the cascade reactions of N-alkoxycarboxamide indoles with diazo homophthalimides. Under different conditions, two different types of IISIQ compounds, IISIQ-OR and IISIQ-H, were formed. This method provides a versatile approach for the synthesis of diverse spiroheterocyclic scaffolds.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Lei Tang, Yuanjiu Xiao, Feng Wu, Jin-Lan Zhou, Tong-Tong Xu, Jian-Jun Feng
Summary: A silver-catalyzed dearomative cycloaddition strategy is described for the synthesis of indoline fused BCHs. It has high yields, wide functional group tolerance, and provides unexplored chemical space for drug design and development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yong-Liang Su, Kuiyong Dong, Haifeng Zheng, Michael P. Doyle
Summary: A new catalytic methodology for synthesizing pyrazolines from alpha-diazo compounds and conjugated alkenes was reported. The regiocontrolled addition of diazomethyl radicals to carbon-carbon double bonds followed by intramolecular ring closure and tautomerization achieved a diverse set of pyrazolines in good yields with excellent regioselectivity. This strategy overcomes the limitations of electron-deficient alkenes and opens new opportunities for versatile transformations of diazo compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Cheng Wang, Guangyang Xu, Ying Shao, Shengbiao Tang, Jiangtao Sun
Article
Chemistry, Multidisciplinary
Kai Wang, Jianliang Yu, Ying Shao, Shengbiao Tang, Jiangtao Sun
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Organic
Xiaofeng Liu, Ying Shao, Jiangtao Sun
Summary: A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, providing N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to this unprecedented reaction is the use of CpRu(PPh3)(2)Cl as the catalyst and sulfoxonium ylides as the alkylation reagents, which can also be applied to 7-azaindoles with slight variations in reaction conditions. Furthermore, sulfonium ylides are also suitable alkylation reagents for good selectivity in N-alkylation of 2-pyridones.
Article
Chemistry, Organic
Junheng Liu, Guangyang Xu, Shengbiao Tang, Qun Chen, Jiangtao Sun
Article
Chemistry, Organic
Guangyang Xu, Ying Shao, Shengbiao Tang, Qun Chen, Jiangtao Sun
Article
Chemistry, Organic
Yong Xu, Jiangtao Sun
Summary: This study describes the use of gold-catalyzed cascade cyclization and 1,3-difunctionalization of 2-(1-alkyny)-2-alken-1-ones with N,O-acetals, leading to the discovery of novel 1,3-oxyaminomethylation and 1,3-aminomethylamination. By varying reaction conditions, particularly the gold catalysts, these two distinct reaction pathways can be selectively controlled. Tandem cyclization and 1,4-oxyaminomethylation have also been achieved.
Article
Chemistry, Organic
Ziyong Li, Jiangtao Sun
Summary: This reaction allows for the preparation of trisubstituted alkenylboronates through a copper-catalyzed three-component reaction, selectively occurring at the terminal carbon atom and proceeding through a complex tandem sequence. The copper catalyst plays a crucial role in the process by facilitating both the initial cross-coupling and the subsequent stereoselective boration reaction, with different carbene precursors leading to Z- and E-alkenes selectively.
Article
Chemistry, Multidisciplinary
Kai Wang, Ziye Liu, Guangyang Xu, Ying Shao, Shengbiao Tang, Ping Chen, Xinhao Zhang, Jiangtao Sun
Summary: Asymmetric carbene insertion reactions are crucial for constructing carbon-heteroatom bonds, but high enantioselectivity typically requires the use of donor-acceptor diazo compounds with an ester group. This study presents the first chemo and enantioselective formal N-H insertion of 2-pyridones using enynones as donor-donor carbene precursors, with DFT calculations revealing an unprecedented enantioselective 1,4-proton transfer from O to C. The rhodium catalyst's chiral pocket, along with steric repulsion and pi-pi interactions of the propeller ligand, play essential roles in determining the selectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Guangyang Xu, Zhen Wang, Ying Shao, Jiangtao Sun
Summary: An enantioselective copper-catalyzed tandem cross-coupling/alkynylogous aldol reaction has been developed, yielding tetrasubstituted allenoates with central and axial chirality. This protocol utilizes copper(II) salts as a catalytic precursor, distinguishing it from previous methods using Cu(I) salts.
Article
Chemistry, Organic
Yong Xu, Zhen Wang, Jiangtao Sun
Summary: The study demonstrates the enantioselective [3 + 1]-cycloaddition of two structurally different diazo compounds using chiral bisoxazoline copper(I) complexes as catalysts, leading to a novel route for the synthesis of cyclobutenes with a quaternary stereocenter. This reaction is the first example of asymmetric cross-electrophile coupling of two diazo substrates via carbene discrimination.
Article
Chemistry, Multidisciplinary
Ziyong Li, Ying Chen, Chuang Wang, Guangyang Xu, Ying Shao, Xinhao Zhang, Shengbiao Tang, Jiangtao Sun
Summary: The atroposelective synthesis of biaryl atropisomers via asymmetric C(sp(2))-H bond insertion reaction of arenes under rhodium catalysis has been achieved, providing moderate to excellent yields with good enantiomeric ratios. Further investigation suggests that this type of axially biaryl scaffold may have promising potentials in developing novel chiral ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xiaozhou Xie, Jiangtao Sun
Summary: The catalyst-free reaction described in this study allows for the straightforward synthesis of 1,5-dihydro-2H-benzo[b]azepin-2-ones under mild reaction conditions, with a broad substrate scope and good functional group tolerance. Additionally, a series of pyridoazepinones have been prepared using N-pyridinyl sulfilimine as the substrate.
Article
Chemistry, Organic
Jiahui Su, Qiongya Li, Ying Shao, Jiangtao Sun
Summary: An enantioselective cyclopropanation reaction of N-substituted 2-pyridones with diazo compounds has been successfully achieved using a chiral rhodium complex as the catalyst, leading to the formation of chiral cyclopropanes with high enantioselectivities and good yields. Additionally, a novel 1,4-rearrangement of a Boc group from N to C has been discovered under rhodium catalysis when using acceptor-acceptor dimethyl 2-diazomalonate as the carbene precursor.
Article
Chemistry, Organic
Guangyang Xu, Meirong Huang, Tao Zhang, Ying Shao, Shengbiao Tang, He Cao, Xinhao Zhang, Jiangtao Sun
Summary: In this study, an enantioselective insertion of a carbene into the Csp2-H bond of anisole derivatives was achieved using a chiral gold complex and a chiral phosphoric acid as the catalytic system, offering a novel approach for the synthesis of chiral α,α-diarylacetates.
Article
Chemistry, Multidisciplinary
Shengbiao Tang, Peng Zhang, Changkai Wang, Ying Shao, Jiangtao Sun
Summary: The report introduces a new iridium-catalyzed reaction with free carboxylic acids as nucleophiles for synthesizing chiral compounds from racemic secondary allylic alcohols. This method shows excellent regio- and enantioselectivity under mild conditions, allowing for a broad functional group tolerance.
CHEMICAL COMMUNICATIONS
(2021)
