Article
Chemistry, Organic
Brianna M. Bembenek, Maya M. S. Petersen, Julia A. Lilly, Amber L. Haugen, Naomi J. Jiter, Andrew J. Johnson, Ethan E. Ripp, Shelby A. Winchell, Alisha N. Harvat, Caitlin McNulty, Sierra A. Thein, Abbigail M. Grieger, Brandon J. Lyle, Gabriella L. Mraz, Abigail M. Stitgen, Samuel Foss, Merranda L. Schmid, Joseph D. Scanlon, Patrick H. Willoughby
Summary: This study focuses on the generation of complex molecules with diverse functionality using two aryne intermediates. By synthesizing aryl phosphonates through specific methods, the research demonstrates the usefulness of these compounds in medicinal chemistry and materials science. Moreover, the regioselectivity of aryne trapping reactions can be tuned by simply changing the solvent, showcasing the versatility and control of the reaction process.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Haoyin Yuan, Wenhao Yin, Jili Hu, Yang Li
Summary: In this paper, an efficient aryne generation protocol is developed, which involves ortho-deprotonative elimination from 3-sulfonyloxyaryl(mesityl)iodonium triflates. The generated 3-sulfonyloxyarynes can serve as efficient 1,2-benzdiyne synthons, allowing for the preparation of highly functionalized analogues with high functional group tolerance and dense substitution. Carbonate and fluoride salts are found to be efficient activating reagents, acting as the weakest bases used in ortho-deprotonative elimination strategies.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jiarong Shi, Lianggui Li, Chunhui Shan, Junli Wang, Zhonghong Chen, Rongrong Gu, Jia He, Min Tan, Yu Lan, Yang Li
Summary: An unprecedented aryne 1,2,3,5-tetrasubstitution was achieved through a reaction involving 3-silylbenzyne and aryl allyl sulfoxide. The mechanism includes regioselective aryne insertion into the S=O bond, [3,6]-sigmatropic rearrangement, and thermal aromatic 1,3-silyl migration cascade.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Thomas Sephton, Anastasios Charitou, Cristina Trujillo, Jonathan M. Large, Sam Butterworth, Michael F. Greaney
Summary: This study found that benzyne can be used to activate anilines and set up aryl transfer reactions in a single step, establishing a metal-free route to valuable biaryl products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shiwei Lu, Zipeng Wang, Xiang Gao, Kai Chen, Shifa Zhu
Summary: This study presents a method for directly inserting acetylene into readily available bifunctional reagents, resulting in high regio- and stereoselective synthesis of diverse C2-linked 1,2-bis-heteroatom products and opening up new synthetic directions. The synthetic potential of the method was demonstrated by converting the obtained products into various functionalized molecules and chiral sulfoxide-containing bidentate ligands. The mechanism for this insertion reaction was investigated using a combination of experimental and theoretical methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haruki Mizoguchi, Hidetoshi Kamada, Kazuki Morimoto, Ryuji Yoshida, Akira Sakakura
Summary: A stereoselective annulative coupling reaction that forms two C-C bonds and one C-B bond has been developed. This reaction utilizes a 1,2-metallate rearrangement of boronate triggered by the addition of a vinyl group to an aryne. The resulting annulated borinic ester can be converted to various boronic acids and their derivatives, with site-selective halogenation and Suzuki-Miyaura coupling reactions producing highly substituted alkylboronic acid derivatives.
Article
Chemistry, Multidisciplinary
Bastien Delayre, Qian Wang, Jieping Zhu
Summary: The art of natural product total synthesis is closely associated with the development of novel chemical reactions and strategic use of classic organic reactions. New synthetic methods and domino processes can lead to concise synthesis routes for natural products.
ACS CENTRAL SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Satoshi Minakata, Hayato Miwa, Kenya Yamamoto, Arata Hirayama, Sota Okumura
Summary: This study demonstrates the stereospecific, substrate-controlled intermolecular anti- and syn-1,2-diaminations of unactivated alkenes using an iodine catalyst. The combined use of the two methods allows access to all diastereomeric forms of 1,2-diamines, even in the presence of E- and Z-alkenes, with the resulting products easily convertible into free vicinal diamines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Li Chen, Shengtong Niu, Shouang Lan, Wenjun Liu, Shuang Yang, Xinqiang Fang
Summary: Two unprecedented trifunctionalization reactions of ynones have been achieved using organic phosphine catalysis under mild and environmentally benign conditions. By using (PrOH)-Pr-i as the solvent, a range of valuable compounds were synthesized with high stereoselectivity. Uncommon bond cleavage and formation processes were observed, demonstrating the robustness of organocatalysis in facilitating complex transformations.
Article
Chemistry, Multidisciplinary
Jian-Fei Ge, Xi-Zhang Zou, Xin-Ru Liu, Chong-Lei Ji, Xin-Yuan Zhu, De-Wei Gao
Summary: Efficient asymmetric allylic alkylation reactions triggered by 1,2-boron shift have been developed, providing valuable organoboronates. The enantioselective reactions were achieved through a dynamic kinetic resolution process of allylic carbonates at elevated temperature. The research also demonstrated the diversification of (bis-boryl)alkenes to access versatile molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hui Wang, Wangyujing Han, Adam Noble, Varinder K. Aggarwal
Summary: This study reports a nickel/photoredox-catalyzed site-selective mono-deboronative arylation of 1,2-bis-boronic esters, which allows for selective coupling of the more sterically hindered secondary/tertiary positions. This is achieved by utilizing a 1,2-boron shift of primary β-boryl radicals to the thermodynamically favored secondary/tertiary radicals for arylation. The mild conditions of this method are suitable for a wide range of aryl halides, resulting in good yields and high regioselectivity. Additionally, this method allows for stereodivergent coupling of cyclic cis-1,2-bis-boronic esters to give trans-substituted products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Constanze Keck, Jennifer Hahn, Divanshu Gupta, Holger F. Bettinger
Summary: This study reveals a highly acidic boron-nitrogen compound that can interact with silicon-containing compounds and activate their silicon bonds, providing insights into the insertion reaction mechanism.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Simon B. H. Karnbrock, Christopher Golz, Ricardo A. Mata, Manuel Alcarazo
Summary: We describe the synthesis of a nearly square-pyramidal chlorophosphorane supported by a tetradentate bis(amidophenolate) ligand. The resulting phosphonium cation efficiently facilitates the disproportionation of 1,2-diphenylhydrazine to aniline and azobenzene. Mechanistic studies suggest that the high electrophilicity of the cationic P-V center induced by the geometry constraints of the rigid pincer ligand, combined with the electron reservoir ability of the o-amidophenolate moieties, contributes to this unprecedented reactivity mode for P-V centers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Constanze Keck, Jennifer Hahn, Divanshu Gupta, Holger F. Bettinger
Summary: The research demonstrates that the boron-nitrogen analogue of ortho-benzyne is a reactive intermediate capable of interacting with silicon-containing single bonds and even activating and inserting into very strong Si-F bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Yao Zhu, Hai-Yang Huang, Yong-Qin He, Mei Wang, Xiao-Yu Wang, Xian-Rong Song, Zhi-Jie Mao, Wan-Fa Tian, Qiang Xiao
Summary: Here, we present a visible-light enabled platform for the photochemical reduction of 1,2-dicarbonyl compounds to alpha-hydroxy carbonyl derivatives using diisopropylethylamine as a reductant. This reaction shows tolerance towards various fragile groups such as methylthio, halogens, cyano, and heterocycles. Experimental studies and DFT calculations confirm a double hydrogen atom transfer (HAT) pathway.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Dan Liu, Kai Yang, Di Fang, Shi-Jun Li, Yu Lan, Yiyun Chen
Summary: This study reports the first method for generating formyl radicals from alpha-chloro N-methoxyphthalimides, which selectively synthesize aldehydes under mild photoredox conditions. The method exhibits excellent chemoselectivity and regioselectivity for installing aldehydes on various organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Xinghua Wang, Ya-Nan Wang, Zhipeng Pei, Shi-Jun Li, Donghui Wei, Yu Lan
Summary: Great success has been achieved in the precise construction of C-C bonds under N-heterocyclic carbene (NHC)/ Bronsted acid (BA) cooperative catalysis. However, the mechanism behind the acceleration of conversions of alpha,beta-unsaturated carbonyls by NHC and BA co-catalyst remains unclear. In this study, several representative NHC/BA cooperative catalysis models were systematically studied to enhance chemists' understanding of these reactions. The identification and confirmation of favorable models for the NHC/BA cooperatively catalyzed reactions of alpha,beta-unsaturated carbonyls were done using proposed combination rules of hydrogen bond donor/acceptor-electrophile/nucleophile and reactivity index (Rk). This work is significant for comprehending the cooperative catalytic mechanism and provides valuable insights for designing efficient cooperative catalytic reactions with specific selectivity.
Article
Chemistry, Multidisciplinary
Haizhen Wang, Di Liu, Haifeng Chen, Yuqing Jiao, Haixin Zhao, Zongcheng Li, Siyuan Hou, Yanli Ni, Rong Zhang, Jinyong Wang, Jie Zhou, Bing Liu, Yu Lan
Summary: During the development of mid-gestational mouse embryos, specialized endothelial cells called hemogenic endothelial cells (HECs) differentiate into hematopoietic stem and progenitor cells (HSPCs) through a process called endothelial-to-hematopoietic transition (EHT). This study reveals that the gene Nupr1, previously identified as a signature gene of HECs, negatively regulates the EHT process. Deletion of Nupr1 in endothelial cells leads to increased HSPC generation in the aorta-gonad-mesonephros region. The study also finds that the proinflammatory cytokine TNF-alpha is upregulated in Nupr1-deficient HECs, and neutralizing TNF-alpha partially reduces excessive HSPC generation. These findings suggest that Nupr1 could be a potential target for future research on hematopoietic stem cell regeneration.
Article
Multidisciplinary Sciences
Jun Wu, Shi-Jun Li, Long Jiang, Xiao-Chi Ma, Yu Lan, Li Shen
Summary: This study presents a novel method for late-stage skeletal reorganization (LSSR) of limonoid natural products through photochemical cascades. Nine distinct limonoid products with five unprecedented scaffolds are generated from xyloelves A and B. Quantum mechanical calculations reveal the photocascade pathways and mechanistic rationale of these natural products. Notably, a UV light-driven transannular and stereoselective C -> C 1,4-acyl migration is discovered as a photochemical approach for LSSR, which shows potential for accessing bioactive cage-like molecules. Additionally, the findings provide a proof of concept for natural product photobiosynthesis, and xyloelf A can be used as a molecular template for hepatoprotective drug discovery.
Article
Chemistry, Multidisciplinary
Wei Zhang, Li-Li Liao, Li Li, Yi Liu, Long-Fei Dai, Guo-Quan Sun, Chuan-Kun Ran, Jian-Heng Ye, Yu Lan, Da-Gang Yu
Summary: The dicarboxylation of unactivated skipped dienes with CO2 via electrochemistry is reported for the first time, providing valuable dicarboxylic acids. Control experiments and DFT calculations confirm the single electron transfer reduction of CO2 to its radical anion, followed by sluggish radical addition to unactivated alkenes, SET reduction of unstabilized alkyl radicals to carbanions, and nucleophilic attack on CO2 to give the desired products. This reaction possesses mild reaction conditions, broad substrate scope, facile derivations of products, and promising application in polymer chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kangbao Zhong, Shihan Liu, Xiaoqian He, Hao Ni, Wei Lai, Wenting Gong, Chunhui Shan, Zhuang Zhao, Yu Lan, Ruopeng Bai
Summary: This report describes the oxidative cyclopalladation activation of a C =C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway involves an oxidative cyclopalladation to generate a pallada-cyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. Theoretical calculations indicate covalent bonding between a Pd(II) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.
CHINESE CHEMICAL LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Yumeng Shuai, Jianzhong Zhao, Renheng Bo, Yu Lan, Zengyao Lv, Yihui Zhang
Summary: Mechanically-guided three-dimensional assembly is a novel method for fabricating micro/nanoscale 3D structures and devices. It utilizes compressive buckling in a patterned high-modulus thin film integrated with a low-modulus elastomer substrate. To address the challenges of highly flexible 3D mesostructures or those with large-area suspended features, a wrinkling-assisted strategy is proposed to facilitate the delamination at desired regions. This strategy involves introducing an assisting layer with a weaker film/assisting-layer interface and utilizing wrinkles in the assisting layer to induce additional driving forces for separation.
JOURNAL OF THE MECHANICS AND PHYSICS OF SOLIDS
(2023)
Article
Chemistry, Multidisciplinary
Meng Miao, Lei Zhu, Hong Zhao, Lei Song, Si-Shun Yan, Li-Li Liao, Jian-Heng Ye, Yu Lan, Da-Gang Yu
Summary: Difunctionalizing carboxylation of alkynes with CO2 is a sustainable and important strategy to generate valuable acrylate derivatives from readily available starting materials. This study introduces a visible-light-driven and transition metal-free thio-carboxylation of alkynes with thiophenols and CO2. The use of single-electron activation of CO2 leads to unique beta-carboxylation, followed by efficient cyclizing acylation to obtain important thiochromones. The one-pot method features mild reaction conditions, high selectivity, scalability, and facile derivatization of products to bioactive compounds.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Lei Zeng, Shihan Liu, Yu Lan, Lizhu Gao
Summary: This study reports a catalytic asymmetric inverse-electron-demand oxa-Diels-Alder reaction for the synthesis of enantioenriched six-membered oxygen-containing heterocycles. The reaction between α-bromoacroleins and neutral alkenes is catalyzed by oxazaborolidinium cation 1f, leading to the formation of dihydropyrans with high yields and excellent enantioselectivities. The efficient synthesis of (+)-Centrolobine is demonstrated, highlighting the practical utility of this reaction.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Shugao Zhu, Dan Wang, Shihan Liu, Yufeng Ma, Hong Wang, Yu Lan, Ruopeng Bai, Ruwei Shen
Summary: The Pd-catalyzed reaction of 1-(2-iodophenyl)-3-arylprop-2-yn-1-ones with propargyl sulfonamide produces cyclobuta[b]naphthalen-3(1H)-ones, while the reaction with propargyl ethers affords 11H-benzo[b]fluoren-11-ones as products. Experimental and theoretical studies reveal that the former reaction proceeds through Pd-catalyzed cross-coupling, propargyl-allenyl isomerization, and [2 + 2] cycloaddition, while the latter involves Pd-catalyzed cross-coupling, propargylic Alder-ene-type reaction, and 6 pi-electrocyclization leading to the formation of [4 + 2] cycloadducts. The divergent formation of two types of allenic intermediates depending on propargylic substrates is confirmed and elucidated.
Article
Chemistry, Multidisciplinary
Wenqiang Zhou, Song Xi, Haohua Chen, Dan Jiang, Jiao Yang, Shuangwei Liu, Ling He, Hanyue Qiu, Yu Lan, Min Zhang
Summary: Bridged frameworks are important in chemistry and biology, found commonly in pharmaceuticals and natural products. Traditional methods of building these rigid segments at the middle or late stage of synthesis decrease efficiency and specificity. In this study, a novel strategy was used to construct a morphan core equipped with an allene/ketone group through an enantioselective a-allenylation of ketones. The resulting bridged backbone guided the assembly of up to five fusing rings, and the allene and ketone groups allowed precise installation of various functionalities, leading to a concise total synthesis of nine strychnan alkaloids.
Article
Chemistry, Organic
Kai Yang, Jiabin Liu, Dongmin Fu, Linbin Niu, Shi-Jun Li, Yu Lan
Summary: A radical relay model was developed for cross-coupling reactions involving multi-radical systems. The regio- and chemoselectivity of radical addition processes were examined using the photosensitized difunctionalization of styrene with oxime carbonate as a model reaction. In this model mechanism, a photosensitizer molecule absorbs a photon to generate an excited state, which then undergoes a triplet-triplet energy transfer process to produce an excited oxime carbonate intermediate. The chemoselectivity of the cross-coupling reaction is determined by variations in the relative concentrations of the two radical species.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Rong Fan, Shihan Liu, Qiang Yan, Yun Wei, Jingwen Wang, Yu Lan, Jiajing Tan
Summary: Boronic acids are widely used reagents in organic synthesis, and this study demonstrates their potential as efficient substitutes for hydroxides when activated through fluoride complexation. The researchers developed a novel reaction involving aryne-induced ring-opening of cyclic sulfides and three-component coupling of fluoro-azaarenes to showcase this application. The novel hydroxy source exhibits mild activation conditions, useful functionality tolerance, and structural tunability, offering new possibilities for organoboron chemistry. Detailed computational studies shed light on the mechanistic pathway and reactivity differences of ArB(OH)(x)F-y complexes, supporting the experimental data.
Article
Chemistry, Organic
Qianqian Shi, Kuohong Chen, Limin Guo, Lili Han, Donghui Wei, Yu Lan
Summary: In this study, the possible mechanisms of a series of deaminative radical reaction models have been investigated, revealing the existence of relayed proton-coupled electron transfer (relayed-PCET) mechanism instead of the commonly accepted single-electron transfer (SET) mechanism. Various deaminative radicals, including alkyl radicals, trifluoromethyl radicals, N-centered radicals, O-centered radicals, and other related radicals, are formed through homolysis of N-X (X = C, O, N) bonds. The exact orbital overlap pictures associated with different interaction modes and electron localization function (ELF) analysis provide insights into the nature of these deaminative radical reactions. This work is critical for understanding the general principle and detailed mechanism of deaminative radical reactions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jiangliang Yin, Jian Li, Haohua Chen, Ya Wang, Yuming Zhang, Cheng Zhang, Zhengyang Bin, Daniel Pyle, Yudong Yang, Yu Lan, Jingsong You
Summary: This study reports a programmable zigzag pi-extension strategy based on rhodium-catalysed sequential C2-H and C8-H activation-annulation of naphthalene ketones for rapid assembly of graphene-like molecules. This strategy uses acetylenedicarboxylates as the C2 insertion unit and selectively extends the naphthalene fragment through C(sp3)-H cyclization. The synthesis of related products such as anthanthrene and peri-naphthacenonaphthacene is successfully achieved.
