Electron-deficient boron-based catalysts for C–H bond functionalisation

Yuanhong Ma, Shao-Jie Lou and Zhaomin Hou

Chem. Soc. Rev., 2021, 50, 1945
DOI: 10.1039/D0CS00380H

Transition metal-catalyzed site- and regio-divergent C–H bond functionalization

Lucy Ping, Da Sol Chung, Jean Bouffard and Sang-gi Lee

Chem. Soc. Rev., 2017, 46, 4299
DOI: 10.1039/C7CS00064B

B(C6F5)3-Catalyzed cyclization of alkynes: direct synthesis of 3-silyl heterocyclic compounds

Mengxing Li, Ting Wang, Zhenyu An and Rulong Yan

Chem. Commun., 2020, 56, 11953
DOI: 10.1039/D0CC04314A

Catalytic metal-free Si–N cross-dehydrocoupling

Lutz Greb, Sergej Tamke and Jan Paradies

Chem. Commun., 2014, 50, 2318
DOI: 10.1039/C3CC49558B

B(C6F5)3-Catalyzed redox-neutral β-alkylation of tertiary amines using p-quinone methides via borrowing hydrogen

Rui Li, Yong Chen, Kun Jiang, Feiyi Wang, Cuifen Lu, Junqi Nie, Zuxing Chen, Guichun Yang, Ying-Chun Chen, Yu Zhao and Chao Ma

Chem. Commun., 2019, 55, 1217
DOI: 10.1039/C8CC09215J

Comparative DFT study of metal-free Lewis acid-catalyzed C–H and N–H silylation of (hetero)arenes: mechanistic studies and expansion of catalyst and substrate scope

Pan Du and Jiyang Zhao

RSC Adv., 2019, 9, 37675
DOI: 10.1039/C9RA07985H

Deoxygenative CO2 conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

Takumi Murata, Mahoko Hiyoshi, Shinsuke Maekawa, Yuta Saiki, Manussada Ratanasak, Jun-ya Hasegawa and Tadashi Ema

Green Chem., 2022, 24, 2385
DOI: 10.1039/D1GC04599G

Facile synthesis of tribenzosilepins from terphenyls and dihydrosilanes by electrophilic double silylation

Yafang Dong, Kohei Sekine and Yoichiro Kuninobu

Chem. Commun., 2021, 57, 7007
DOI: 10.1039/D1CC02326H

B(C6F5)3-Promoted hydrogenations of N-heterocycles with ammonia borane

Fangwei Ding, Yiliang Zhang, Rong Zhao, Yanqiu Jiang, Robert Li-Yuan Bao, Kaifeng Lin and Lei Shi

Chem. Commun., 2017, 53, 9262
DOI: 10.1039/C7CC04709F

A unified survey of Si–H and H–H bond activation catalysed by electron-deficient boranes

Martin Oestreich, Julia Hermeke and Jens Mohr

Chem. Soc. Rev., 2015, 44, 2202
DOI: 10.1039/C4CS00451E

Dual reactivity of B(C6F5)3 enables the silylative cascade conversion of N-aryl piperidines to sila-N-heterocycles: DFT calculations

Miaomiao Zhou, Sehoon Park and Li Dang

Org. Chem. Front., 2020, 7, 944
DOI: 10.1039/C9QO01437C

Emerging Strategies for C–H Silylation

Sven C. Richter and Martin Oestreich

Trends in Chemistry, 2020, 2, 13
DOI: 10.1016/j.trechm.2019.07.003

Dehydrogenative Annulation of Silylated 1H-Indoles with Alkynes via Silyl Migration

Hidekazu Arii, Daisuke Nakane, Kenichi Nakao, Hideki Masuda and Takayuki Kawashima

Org. Lett., 2023, 25, 5416
DOI: 10.1021/acs.orglett.3c01650

NHC-Copper-Catalyzed Asymmetric Dearomative Silylation of Indoles

Yongjia Shi, Qian Gao and Senmiao Xu

J. Org. Chem., 2018, 83, 14758
DOI: 10.1021/acs.joc.8b02308

Metal‐Free Arene and Heteroarene Borylation Catalyzed by Strongly Electrophilic Bis‐boranes

Yun‐Lin Liu, Gerald Kehr, Constantin G. Daniliuc and Gerhard Erker

Chemistry A European J, 2017, 23, 12141
DOI: 10.1002/chem.201701771

Transition‐Metal‐Free C−H Silylation: An Emerging Strategy

Aparna Tyagi, Naveen Yadav, Jabir Khan, Sanjay Singh and Chinmoy Kumar Hazra

Asian J Org Chem, 2021, 10, 334
DOI: 10.1002/ajoc.202000584

Zinc-Catalyzed Dehydrogenative Silylation of Indoles

Kyohei Yonekura, Yoshihiko Iketani, Masaru Sekine, Tomohiro Tani, Fumiya Matsui, Daiki Kamakura and Teruhisa Tsuchimoto

Organometallics, 2017, 36, 3234
DOI: 10.1021/acs.organomet.7b00382

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

Hendrik F. T. Klare, Lena Albers, Lars Süsse, Sebastian Keess, Thomas Müller and Martin Oestreich

Chem. Rev., 2021, 121, 5889
DOI: 10.1021/acs.chemrev.0c00855

Switchable C–H Silylation of Indoles Catalyzed by a Thermally Induced Frustrated Lewis Pair

Yuxi Han, Sutao Zhang, Jianghua He and Yuetao Zhang

ACS Catal., 2018, 8, 8765
DOI: 10.1021/acscatal.8b01847

Transition‐Metal‐Free Direct C−H Silylation of Electron‐Deficient Heteroarenes with Hydrosilanes via a Radical Mechanism

Ryu Sakamoto, Bich‐Ngoc Nguyen and Keiji Maruoka

Asian J Org Chem, 2018, 7, 1085
DOI: 10.1002/ajoc.201800282

Silylation of C–H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

Anton A. Toutov, Wen-Bo Liu, Kerry N. Betz, Alexey Fedorov, Brian M. Stoltz and Robert H. Grubbs

Nature, 2015, 518, 80
DOI: 10.1038/nature14126

B(C6F5)3‐Catalyzed Reduction of Cyclic N‐Sulfonyl Ketimines

Lei Shi, Robert Li‐Yuan Bao, Limin Zheng and Rong Zhao

Eur J Org Chem, 2019, 2019, 6550
DOI: 10.1002/ejoc.201900706

Di-tert-butyl Peroxide (DTBP)-Mediated Oxysilylation of Unsaturated Carboxylic Acids for the Synthesis of Silyl Lactones

Kanako Nozawa-Kumada, Takuto Ojima, Moeto Inagi, Masanori Shigeno and Yoshinori Kondo

Org. Lett., 2020, 22, 9591
DOI: 10.1021/acs.orglett.0c03640

Unlocking a Nano-Aluminum Oxide Lewis Acid Layer as the Electrocatalyst for Hydrogenation of Thiophene and Other Arenes

Xiaofeng Zhang, Aoqian Qiu, Pan Ran, Mengning Ding and Xu Cheng

J. Am. Chem. Soc., 2025, 147, 23797
DOI: 10.1021/jacs.5c06034

(Aminomethyl)pyridine Complexes for the Cobalt‐Catalyzed Anti‐Markovnikov Hydrosilylation of Alkoxy‐ or Siloxy(vinyl)silanes with Alkoxy‐ or Siloxyhydrosilanes

Kangsang L. Lee

Angew Chem Int Ed, 2017, 56, 3665
DOI: 10.1002/anie.201612460

B(C6F5)3-Catalyzed (Convergent) Disproportionation Reaction of Indoles

Yuxi Han, Sutao Zhang, Jianghua He and Yuetao Zhang

J. Am. Chem. Soc., 2017, 139, 7399
DOI: 10.1021/jacs.7b03534

Deprotonative Silylation of Aromatic C–H Bonds Mediated by a Combination of Trifluoromethyltrialkylsilane and Fluoride

Kanako Nozawa-Kumada, Sayuri Osawa, Midori Sasaki, Isabelle Chataigner, Masanori Shigeno and Yoshinori Kondo

J. Org. Chem., 2017, 82, 9487
DOI: 10.1021/acs.joc.7b01525

Durch Nichtedelmetallsalze ausgelöste Friedel‐Crafts‐artige intermolekulare C‐H‐Silylierung von elektronenreichen Arenen

Qin Yin, Hendrik F. T. Klare and Martin Oestreich

Angewandte Chemie, 2016, 128, 3256
DOI: 10.1002/ange.201510469

Synthesis and structural characterization of selected silylated or germylated pyrazoleboronic acids

Krzysztof Durka, Agnieszka Górska, Tomasz Kliś, Marcin Kublicki, Janusz Serwatowski and Krzysztof Woźniak

Tetrahedron Letters, 2015, 56, 1855
DOI: 10.1016/j.tetlet.2015.02.089

B(C6F5)3/Amine‐Catalyzed C(sp)−H Silylation of Terminal Alkynes with Hydrosilanes: Experimental and Theoretical Studies

Yuanhong Ma, Shao‐Jie Lou, Gen Luo, Yong Luo, Gu Zhan, Masayoshi Nishiura, Yi Luo and Zhaomin Hou

Angewandte Chemie, 2018, 130, 15442
DOI: 10.1002/ange.201809533

Free-Radical-Promoted Site-Selective C–H Silylation of Arenes by Using Hydrosilanes

Zhengbao Xu, Li Chai and Zhong-Quan Liu

Org. Lett., 2017, 19, 5573
DOI: 10.1021/acs.orglett.7b02717

Übergangsmetallfreie ringöffnende Silylierung von Indolen und Benzofuranen mit (Diphenyl‐tert‐butylsilyl)lithium

Pan Xu, Ernst‐Ulrich Würthwein, Constantin G. Daniliuc and Armido Studer

Angewandte Chemie, 2017, 129, 14060
DOI: 10.1002/ange.201707309

Rhodium hydride enabled enantioselective intermolecular C–H silylation to access acyclic stereogenic Si–H

Kun An, Wenpeng Ma, Li-Chuan Liu, Tao He, Guiyu Guan, Qing-Wei Zhang and Wei He

Nat Commun, 2022, 13
DOI: 10.1038/s41467-022-28439-w

Highly Stereoselective Metal-Free Hydrogenations of Pyrrolo[1,2-a]quinoxalines

Xiaoqin Liu, Ting Liu, Wei Meng and Haifeng Du

Org. Lett., 2018, 20, 5653
DOI: 10.1021/acs.orglett.8b02364

A Pincer Ruthenium Complex for Regioselective C–H Silylation of Heteroarenes

Huaquan Fang, Le Guo, Yuxuan Zhang, Wubing Yao and Zheng Huang

Org. Lett., 2016, 18, 5624
DOI: 10.1021/acs.orglett.6b02857

Boron-Catalyzed O–H Bond Insertion of α-Aryl α-Diazoesters in Water

Htet Htet San, Shi-Jun Wang, Min Jiang and Xiang-Ying Tang

Org. Lett., 2018, 20, 4672
DOI: 10.1021/acs.orglett.8b01988

Catalytic Access to Indole-Fused Benzosiloles by 2-Fold Electrophilic C–H Silylation with Dihydrosilanes

Lukas Omann and Martin Oestreich

Organometallics, 2017, 36, 767
DOI: 10.1021/acs.organomet.6b00801

B(C6F5)3‐Catalyzed Transfer Hydrogenation of Imines and Related Heteroarenes Using Cyclohexa‐1,4‐dienes as a Dihydrogen Source

Indranil Chatterjee and Martin Oestreich

Angew Chem Int Ed, 2015, 54, 1965
DOI: 10.1002/anie.201409246

Catalytic Access to Bridged Sila-N-heterocycles from Piperidines via Cascade sp3 and sp2 C–Si Bond Formation

Jianbo Zhang, Sehoon Park and Sukbok Chang

J. Am. Chem. Soc., 2018, 140, 13209
DOI: 10.1021/jacs.8b08733

Organocatalysis in Inert C–H Bond Functionalization

Yan Qin, Lihui Zhu and Sanzhong Luo

Chem. Rev., 2017, 117, 9433
DOI: 10.1021/acs.chemrev.6b00657

B(C6F5)3-Catalyzed β-Functionalization of Pyrrolidines Using Isatins via Borrowing Hydrogen: Divergent Access to Substituted Pyrrolidines and Pyrroles

Yong Chen, Hai-Lun Wan, Yuan Huang, Song Liu, Feiyi Wang, Cuifen Lu, Junqi Nie, Zuxing Chen, Guichun Yang and Chao Ma

Org. Lett., 2020, 22, 7797
DOI: 10.1021/acs.orglett.0c02600

C–H Bond Silylation of Heteroarenes

Hillol Khatua, Subrata Das, Sima Patra and Buddhadeb Chattopadhyay

Synthesis, 2023, 55, 3434
DOI: 10.1055/a-2110-4581

Katalytische Desaromatisierung von N‐Heteroarenen mit Silicium‐ und Borverbindungen

Sehoon Park and Sukbok Chang

Angewandte Chemie, 2017, 129, 7828
DOI: 10.1002/ange.201612140

Boron‐Catalyzed Dehydrative Friedel‐Crafts Alkylation of Arenes Using β‐Hydroxyl Ketone as MVK Precursor

Htet Htet San, Jie Huang, Seinn Lei Aye and Xiang‐Ying Tang

Adv Synth Catal, 2021, 363, 2386
DOI: 10.1002/adsc.202001269

Elektrophile aromatische Substitution mit Siliciumelektrophilen: die katalytische Friedel‐Crafts‐C‐H‐Silylierung

Susanne Bähr and Martin Oestreich

Angewandte Chemie, 2017, 129, 52
DOI: 10.1002/ange.201608470

B(C6F5)3‐katalysierte Transferhydrierung von Iminen und verwandten Heteroaromaten mit Cyclohexa‐1,4‐dienen als Wasserstoffquelle

Indranil Chatterjee and Martin Oestreich

Angewandte Chemie, 2015, 127, 1988
DOI: 10.1002/ange.201409246

(Aminomethyl)pyridine Complexes for the Cobalt‐Catalyzed Anti‐Markovnikov Hydrosilylation of Alkoxy‐ or Siloxy(vinyl)silanes with Alkoxy‐ or Siloxyhydrosilanes

Kangsang L. Lee

Angewandte Chemie, 2017, 129, 3719
DOI: 10.1002/ange.201612460

Catalytic Dearomatization of N‐Heteroarenes with Silicon and Boron Compounds

Sehoon Park and Sukbok Chang

Angew Chem Int Ed, 2017, 56, 7720
DOI: 10.1002/anie.201612140

Cationic silicon Lewis acids in catalysis

Johannes C. L. Walker, Hendrik F. T. Klare and Martin Oestreich

Nat Rev Chem, 2019, 4, 54
DOI: 10.1038/s41570-019-0146-7

Transition‐Metal‐Free Ring‐Opening Silylation of Indoles and Benzofurans with (Diphenyl‐tert‐butylsilyl)lithium

Pan Xu, Ernst‐Ulrich Würthwein, Constantin G. Daniliuc and Armido Studer

Angew Chem Int Ed, 2017, 56, 13872
DOI: 10.1002/anie.201707309

Mechanistic Insights into Ru–S Complex-Catalyzed C–H Silylation and Borylation of N-Heteroarene: Distinct Bonding Interactions

Naphol Witayapaisitsan, Thanapat Worakul and Panida Surawatanawong

Inorg. Chem., 2025, 64, 4090
DOI: 10.1021/acs.inorgchem.4c05517

B(C6F5)3-Catalyzed Synthesis of Benzofused-Siloles

Liam D. Curless and Michael J. Ingleson

Organometallics, 2014, 33, 7241
DOI: 10.1021/om501033p

B(C6F5)3-Catalyzed Silylation of Unsaturated Hydrocarbons

Xiangqing Feng and Haifeng Du

Chinese Journal of Organic Chemistry, 2023, 43, 3544
DOI: 10.6023/cjoc202306009

Brønsted Acid-Promoted Formation of Stabilized Silylium Ions for Catalytic Friedel–Crafts C–H Silylation

Qing-An Chen, Hendrik F. T. Klare and Martin Oestreich

J. Am. Chem. Soc., 2016, 138, 7868
DOI: 10.1021/jacs.6b04878

Iridium-Catalyzed Regioselective C(sp3)–H Silylation of 4-Alkylpyridines at the Benzylic Position with Hydrosilanes Leading to 4-(1-Silylalkyl)pyridines

Yoshiya Fukumoto, Masaya Hirano and Naoto Chatani

ACS Catal., 2017, 7, 3152
DOI: 10.1021/acscatal.7b00539

Transition-Metal-Free Silylation of Unactivated C(sp2)–H Bonds with tert-Butyl-Substituted Silyldiazenes

Baptiste Neil, Franck Lucien, Louis Fensterbank and Clément Chauvier

ACS Catal., 2021, 11, 13085
DOI: 10.1021/acscatal.1c03824

Selective Silylative Reduction of Pyridines Leading to Structurally Diverse Azacyclic Compounds with the Formation of sp3 C–Si Bonds

Narasimhulu Gandhamsetty, Sehoon Park and Sukbok Chang

J. Am. Chem. Soc., 2015, 137, 15176
DOI: 10.1021/jacs.5b09209

Boron-Catalyzed Aromatic C–H Bond Silylation with Hydrosilanes

Yuanhong Ma, Baoli Wang, Liang Zhang and Zhaomin Hou

J. Am. Chem. Soc., 2016, 138, 3663
DOI: 10.1021/jacs.6b01349

B(C6F5)3/Amine‐Catalyzed C(sp)−H Silylation of Terminal Alkynes with Hydrosilanes: Experimental and Theoretical Studies

Yuanhong Ma, Shao‐Jie Lou, Gen Luo, Yong Luo, Gu Zhan, Masayoshi Nishiura, Yi Luo and Zhaomin Hou

Angew Chem Int Ed, 2018, 57, 15222
DOI: 10.1002/anie.201809533

Electrophilic Aromatic Substitution with Silicon Electrophiles: Catalytic Friedel–Crafts C−H Silylation

Susanne Bähr and Martin Oestreich

Angew Chem Int Ed, 2017, 56, 52
DOI: 10.1002/anie.201608470

B(C6F5)3‐Catalyzed sp3 C—Si Bond Forming Consecutive Reactions

Sehoon Park

Chin. J. Chem., 2019, 37, 1057
DOI: 10.1002/cjoc.201900240

Rhodium‐Catalyzed Silylative and Germylative Cyclization with Dehydrogenation Leading to 9‐Sila‐ and 9‐Germafluorenes: A Combined Experimental and Computational Mechanistic Study

Masahito Murai, Ryo Okada, Sobi Asako and Kazuhiko Takai

Chemistry A European J, 2017, 23, 10861
DOI: 10.1002/chem.201701579

Friedel–Crafts‐Type Intermolecular C−H Silylation of Electron‐Rich Arenes Initiated by Base‐Metal Salts

Qin Yin, Hendrik F. T. Klare and Martin Oestreich

Angew Chem Int Ed, 2016, 55, 3204
DOI: 10.1002/anie.201510469