毕锡和 - 东北师范大学

个人简介

经历 1996.09 - 2000.07 东北师范大学化学学士 2000.09 - 2006.07 东北师范大学有机化学博士 2006.08 - 2008.12 德国波恩大学凯库勒研究所博士后 2005.07 - 2008.12 东北师范大学化学学院讲师 2009.01 - 东北师范大学化学学院副教授，教授荣誉 2006 德国洪堡基金会研究奖学金 2014 Thieme Chemistry Journals Award 2015 国家自然科学基金委“优青” 2016 教育部“长江学者奖励计划”青年学者 2018 吉林省科学技术奖自然科学一等奖 2019 牛顿高级学者药明康德生命化学研究奖 2023 教育部“长江学者奖励计划”特聘教授

研究领域

N-邻三氟甲基苯磺酰腙卡宾化学重氮化合物反应性丰富，经过一百多年的发展，至今仍是有机合成化学研究的前沿和热点领域。重氮化合物的毒性和爆炸性使得直接或者大规模使用存在安全风险，为重氮替代物的发展提供了无限动力。在众多重氮替代物中，磺酰腙具有稳定易制备、结构多样、操作安全等优点。近二十年来，Aggarwal、王剑波、Barluenga、Valdés、等国内外实验室将磺酰腙与过渡金属催化相结合，极大地推动和繁荣了卡宾化学。传统的N-对甲苯磺酰腙存在分解温度较高（通常>70℃）的问题，限制了其在有机合成应用，尤其是不对称催化等对温度敏感的反应中。如何在温和条件下（如：室温甚至零下）实现磺酰腙的分解与合成转化已经成为磺酰腙化学可持续发展的关键问题。近些年，毕锡和课题组在这一重要问题上取得了突破进展。2018年，该课题组发现并报道了易分解的N-邻三氟甲基苯磺酰腙，其能够在低温（乃至零下40℃）分解释放出不稳定的donor-重氮化合物，为在温和条件下探索donor-重氮化合物的转化提供了可能，开启了重氮卡宾化学的新篇章。银催化有机合成与理论研究过渡金属催化是现代有机合成化学发展的重要推动力，发展新催化剂和新反应是这一前沿领域极为重要的研究内容。多变价、强配位的过渡金属占据主导地位，如：铑、钌、钯、铱、铜、金等，这些金属催化活性高，普遍应用于催化有机合成反应；难变价、弱配位的过渡金属则催化活性低，建立这类金属催化的有机反应比较困难，但是往往呈现催化的独特性，所以探索这类金属的催化潜力十分必要。银就是这样的一类过渡金属，银离子最外层5s为空轨道，又拥有充满的4d(10)轨道，这样的电子结构与轨道特征使得银呈现出显著的特性：它是唯一正一价稳定的过渡金属，与质子具有一定的相似性，一些有机银试剂可以看作是相应的酸等当物；有机银中间体一般不稳定，易于发生脱银质子化；是温和的单电子氧化剂和较弱的路易斯酸；与配体相互作用较弱，存在可逆性；具有生物友好性等。总的来说，银的性质可以用“温和”来概括，这也导致银的催化活性不高，银催化化学发展缓慢，对银的作用缺乏深刻认识，一般泛泛地归结为单电子氧化剂、σ-或π-路易斯酸等，造成对其真正作用的忽视。因此，建立银催化的独特反应体系并揭示其催化原理是过渡金属催化研究的重要问题，也是难点问题。过去十余年间，毕锡和课题组聚焦于银催化性能的探索，开展了银催化有机合成与理论研究，取得了系列创新性成果：建立了具有原始创新性的银催化炔烃氢叠氮化反应，并进一步拓展至炔烃系列多组分反应，被国际同行称为“毕的银催化炔烃氢叠氮化方法学（Bi's Ag(I) catalysed hydroazidation methodology）”；发现了银对异氰以及donor-型重氮的优异活化性能，建立了一系列银催化的卡宾反应；在理论上，归纳总结出银的类质子性和弱配位活化，形成了对银的新认知。这些研究工作丰富了银的催化化学，提升了银的合成用途，展现了银的催化潜力。

近期论文

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Rhodium-Catalyzed Asymmetric Cyclopropanation of Indoles with N-Triftosylhydrazones Caicai He, Wei Song, Dandan Wei, Wei Zhao, Qianfei Yu, Jiaqi Tang, Yongquan Ning*, Karunanidhi Murali, Paramasivam Sivaguru, Graham de Ruiter, Xihe Bi* Angew. Chem. Int. Ed. 2024, e202408220 Silver-Catalyzed Single-Carbon Insertion of Indoles withAcetophenone N‑Triftosylhydrazones Linxuan Li, Hongzhu Chen, Xiaolong Zhang,* Karunanidhi Murali, Qingwen Zhu, Menglin Liu, Hongru Zhang, Valentine Nenajdenko* and Xihe Bi* Org. Lett. 2024, 26, 7207-7211 Tunable molecular editing of indoles with fluoroalkyl carbenes Shaopeng Liu, Yong Yang, Qingmin Song, Zhaohong Liu*, Ying Lu, Zhanjing Wang, Paramasivam Sivaguru, Xihe Bi* Nat. Chem. 2024, 16, 988-997 Controllable Skeletal and Peripheral Editing of Pyrroles with Vinylcarbenes Yong Yang, Qingmin Song, Paramasivam Sivaguru, Zhaohong Liu*, Dan Shi, Tian Tian, Graham de Ruiter, Xihe Bi* Angew. Chem. Int. Ed. 2024, 63, e202401359 Silver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones Linxuan Li, Paramasivam Sivaguru, Dandan Wei, Menglin Liu, Qingwen Zhu, Shuai Dong, Emanuele Casali, Nan Li, Giuseppe Zanoni, Xihe Bi* Nat. Commun. 2024, 15, 1951 Rhodium-Catalyzed One-Carbon Ring Expansion of Aziridines with Vinyl-N-triftosylhydrazones for the Synthesis of 2-Vinyl Azetidines Yongquan Ning, Hongzhu Chen, Yongyue Ning, Jin Zhang, Xihe Bi* Angew. Chem. Int. Ed. 2024, 63, e202318072 Dearomative Insertion of Fluoroalkyl Carbenes into Azoles Leading to Fluoroalkyl Heterocycles with a Quaternary Center Linxuan Li, Yongquan Ning, Hongzhu Chen, Yongyue Ning, Dr. Paramasivam Sivaguru, Peiqiu Liao, Qingwen Zhu, Yong Ji, Graham de Ruiter, Prof. Xihe Bi* Angew. Chem. Int. Ed. 2024, 63, e202313807 Site-Selective C−H Allylation of Alkanes: Facile Access to Allylic Quaternary sp3-Carbon Centers Yong Yang, Shaopeng Liu, Shuang Li, Zhaohong Liu*, Peiqiu Liao, Paramasivam Sivaguru, Ying Lu, Jiaojiao Gao, Xihe Bi* Angew. Chem. Int. Ed. 2023, 62, e202214519 Chapter Two - Silver catalysis in organic synthesis: A computational view Yong Wu, Nils Frank, Qingmin Song, Miao Liu, Edward A. Anderson, Xihe Bi* Adv Organomet Chem. 2023, 80, 39-75. Ligand-enabled silver-catalyzed carbene insertion into the N–H bond of aliphatic and electron-rich aromatic amines Linxuan Li, Paramasivam Sivaguru, Xinyue Han, Swastik Karmakar and Xihe Bi* Org. Chem. Front. 2023, 10, 1746-1753 Silver-Catalyzed Vinylcarbene Insertion into C–C Bonds of 1,3-Diketones with Vinyl-N-triftosylhydrazones Yong Wu, Yongquan Ning*, Xinyue Han, Peiqiu Liao, Ying Xia, Paramasivam Sivaguru, and Xihe Bi* Org. Lett. 2022, 24, 8136–8141 A Carbene Strategy for Progressive (Deutero)Hydrodefluorination of Fluoroalkyl Ketones Xiaolong Zhang, Xinyu Zhang, Qingmin Song, Paramasivam Sivaguru, Zikun Wang, Giuseppe Zanoni, Xihe Bi* Angew. Chem. Int. Ed. 2022, 61, e202116190 The merger of vinyl-N-triftosylhydrazones and silver catalysis to enable stereoselective vinylcyclopropanation of alkenes Yong Yang, Zhaohong Liu, Qingmin Song, Paramasivam Sivaguru, Giuseppe Zanoni, Kuan Wang, Qiaowei Bi, Xihe Bi* Chem Catalysis. 2022, 2, 563–577 Silver-catalyzed site-selective C(sp3)−H benzylation of ethers with N-triftosylhydrazones Zhaohong Liu, Hongwei Wang, Paramasivam Sivaguru, Steven P. Nolan, Qingmin Song, Weijie Yu, Xinyu Jiang, Edward A. Anderson & Xihe Bi* Nat. Commun. 2022, 13, 1674 Defluorinative Carboimination of Trifluoromethyl Ketones Xiaolong Zhang, Yongquan Ning, Zhaohong Liu, Shuang Li, Giuseppe Zanoni, and Xihe Bi* ACS Catal. 2022, 12, 8802–8810 Carbodefluorination of fluoroalkyl ketones via a carbene-initiated rearrangement strategy Linxuan Li, Xinyu Zhang, Yongquan Ning, Xiaolong Zhang, Binbin Liu, Zhansong Zhang, Paramasivam Sivaguru, Giuseppe Zanoni, Shuang Li, Edward A. Anderson & Xihe Bi* Nat. Commun. 2022, 13, 4280 81 Chemoselective carbene insertion into the N−H bonds of NH3·H2O Zhaohong Liu, Yong Yang, Qingmin Song, Linxuan Li, Giuseppe Zanoni, Shaopeng Liu, Meng Xiang, Edward A. Anderson & Xihe Bi* Nat. Commun. 2022, 13, 7649 Computational Insights into Different Mechanisms for Ag-, Cu-, and Pd-Catalyzed Cyclopropanation of Alkenes and Sulfonyl Hydrazones Yong Wu, Shanshan Cao, Iskander Douair, Laurent Maron, Xihe Bi* Chem. Eur. J. 2021, 27, 5999-6006 Silver-catalyzed unstrained C(CO)–alkyl bond scission via [3+2]/retro-[3+2] cycloaddition of ketones with N-isocyanoiminotriphenylphosphorane Zikun Wang, Linxuan Li, Xueying Zhang, Xihe Bi* Sci China Chem. 2021, 64, 1157-1163 Fluoroalkyl N-Triftosylhydrazones as Easily Decomposable Diazo Surrogates for Asymmetric [2 + 1] Cycloaddition: Synthesis of Chiral Fluoroalkyl Cyclopropenes and Cyclopropanes Xinyu Zhang, Chunqi Tian, Zhanjing Wang, Paramasivam Sivaguru, Steven P. Nolan, and Xihe Bi* ACS Catal. 2021, 11, 8527-8537 Synthetic exploration of sulfinyl radicals using sulfinyl sulfones Zikun Wang, Zhansong Zhang, Wanjun Zhao, Paramasivam Sivaguru, Giuseppe Zanoni, Yingying Wang, Edward A. Anderson & Xihe Bi* Nat. Commun. 2021, 12, 5244 Catalytic Asymmetric C(sp3)–H Carbene Insertion Approach to Access Enantioenriched 3-Fluoroalkyl 2,3-Dihydrobenzofurans Xinyu Zhang, Paramasivam Sivaguru, Giuseppe Zanoni, Xinyue Han, Minghui Tong, and Xihe Bi* ACS Catal. 2021, 11, 14293-14301 Defluorinative [4 + 1] annulation of perfluoroalkyl N-mesylhydrazones with primary amines provides 5-fluoroalkyl 1,2,3-triazoles Yongquan Ning, Hongwei Wang, Paramasivam Sivaguru, Shuang Li, Giuseppe Zanoni, Steven P. Nolan and Xihe Bi* Green Chem. 2021, 23, 7976-7981 Cycloaddition of Trifluoroacetaldehyde N-Triftosylhydrazone (TFHZ-Tfs) with Alkynes for Synthesizing 3-Trifluoromethylpyrazoles Hongwei Wang, Yongquan Ning, Yue Sun, Paramasivam Sivaguru, and Xihe Bi* Org. Lett. 2020, 22, 2012-2016 Neighbouring carbonyl group-assisted sequential 1,2-azide and 1,4-oxygen migrations of vinyl azides leading to α-azido ketones Yi Gai, Yongquan Ning, Paramasivam Sivaguru, Xiaomeng Li, Yue Zhao, Jiayi Wu & Xihe Bi* Sci. China Chem. 2020, 63, 460-466 Difluoroacetaldehyde N-Triftosylhydrazone (DFHZ-Tfs) as a Bench-Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane Yongquan Ning, Xinyu Zhang, Yi Gai, Yuanqing Dong, Paramasivam Sivaguru, Yingying Wang, Bhoomireddy Rajendra Prasad Reddy, Giuseppe Zanoni, Xihe Bi* Angew. Chem. lnt. Ed. 2020, 59, 6473-6481 Synthesis of β-Difluoroalkyl Azides via Elusive 1,2-Azide Migration Yongquan Ning, Paramasivam Sivaguru, Giuseppe Zanoni, Edward A. Anderson, Xihe Bi* Chem. 2020, 6, 486-496 AgN3-Catalyzed Hydroazidation of Terminal Alkynes and Mechanistic studies Shanshan Cao, Qinghe Ji, Huaizhi Li, Maolin Pang*, Haiyan Yuan, Jingping Zhang*, and Xihe Bi* J. Am. Chem. Soc. 2020, 142, 7083-7091 computational Studies on Reaction Mechanism of the Catalyst-Controlled Selective Insertion of Metal Carbenoids into c-cand C-H Bonds of 1,3-Dicarbonyl Compounds Shanshan Cao, Zhaohong Liu*, Haiyan Yuan, Liu Yang, Jingping Zhang*, and Xihe Bi* Chin. J. Org. Chem. 2020, 40, 2468-2475 Site-Selective C–H Benzylation of Alkanes with N-Triftosylhydrazones Leading to Alkyl Aromatics Zhaohong Liu, Shanshan Cao, Weijie Yu, Jiayi Wu, Fanhua Yi, Edward A. Anderson, Xihe Bi* Chem. 2020, 6, 2110-2124 Palladium(II)-Catalyzed Cross-Coupling of Diazo Compounds and Isocyanides to Access Ketenimines Zhaohong Liu, Shanshan Cao, Jiayi Wu, Giuseppe Zanoni, Paramasivam Sivaguru, and Xihe Bi** ACS Catal. 2020, 10, 12881-12887