ABSTRACT Frustrated Lewis pairs are compounds containing both Lewis acidic and Lewis basic moieties, where the formation of an adduct is prevented by steric hindrance. They are therefore

highly reactive, and have been shown to be capable of heterolysis of molecular hydrogen, a property that has led to their use in hydrogenation reactions of polarized multiple bonds. Here, we

describe a general approach to the hydrogenation of alkynes to _cis_-alkenes under mild conditions using the unique _ansa_-aminohydroborane as a catalyst. Our approach combines several

reactions as the elementary steps of the catalytic cycle: hydroboration (substrate binding), heterolytic hydrogen splitting (typical frustrated-Lewis-pair reactivity) and facile

$21.58 per issue Learn more Buy this article * Purchase on SpringerLink * Instant access to full article PDF Buy now Prices may be subject to local taxes which are calculated during checkout

ADDITIONAL ACCESS OPTIONS: * Log in * Learn about institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT BEING VIEWED BY OTHERS REGIOSELECTIVE ALIPHATIC C–H

FUNCTIONALIZATION USING FRUSTRATED RADICAL PAIRS Article 05 July 2023 COOPERATIVE TRIPLE CATALYSIS ENABLES REGIOIRREGULAR FORMAL MIZOROKI–HECK REACTIONS Article Open access 13 July 2022

REGIOIRREGULAR AND CATALYTIC MIZOROKI–HECK REACTIONS Article 15 April 2021 REFERENCES * Welch, G. C., San Juan, R. R., Masuda, J. D. & Stephan, D. W. Reversible, metal-free hydrogen

activation. _Science_ 314, 1124–1126 (2006). CAS  PubMed  Google Scholar  * Stephan, D. W. ‘Frustrated Lewis pairs’: a concept for new reactivity and catalysis. _Org. Biomol. Chem._ 6,

1535–1539 (2008). CAS  PubMed  Google Scholar  * Stephan, D. W. & Erker, G. Frustrated Lewis pairs: metal-free hydrogen activation and more. _Angew. Chem. Int. Ed._ 49, 46–76 (2010). CAS

  Google Scholar  * Stephan, D. W. et al. Metal-free catalytic hydrogenation of polar substrates by frustrated Lewis pairs. _Inorg. Chem._ 50, 12338–12348 (2011). CAS  PubMed  Google Scholar

  * Stephan, D. W. ‘Frustrated Lewis pair’ hydrogenations. _Org. Biomol. Chem._ 10, 5740–5746 (2012). CAS  PubMed  Google Scholar  * Sumerin, V. et al. Highly active metal-free catalysts for

hydrogenation of unsaturated nitrogen-containing compounds. _Adv. Synth. Catal._ 353, 2093–2110 (2011). CAS  Google Scholar  * Eros, G. et al. Expanding the scope of metal-free catalytic

hydrogenation through frustrated Lewis pair design. _Angew. Chem. Int. Ed._ 49, 6559–6563 (2010). CAS  Google Scholar  * Xu, B-H. et al. Reaction of frustrated Lewis pairs with conjugated

ynones-selective hydrogenation of the carbon–carbon triple bond. _Angew. Chem. Int. Ed._ 50, 7183–7186 (2011). CAS  Google Scholar  * Mahdi, T., Heiden, Z. M., Grimme, S. & Stephan, D.

W. Metal-free aromatic hydrogenation: aniline to cyclohexyl-amine derivatives. _J. Am. Chem. Soc._ 134, 4088–4091 (2012). CAS  PubMed  Google Scholar  * Greb, L. et al. Metal-free catalytic

olefin hydrogenation: low-temperature H2 activation by frustrated Lewis pairs. _Angew. Chem. In. Ed._ 51, 10164–10168 (2012). CAS  Google Scholar  * Köster, R. Neue präparative Möglichkeiten

in der Bor- und Silicium-Chemie. _Angew. Chem._ 68, 383 (1956). Google Scholar  * Köster, R., Bruno, G. & Binger, P. Borverbindungen, V Hydrierung von Bortrialkylen und -triarylen.

_Justus Liebigs Ann. Chem._ 644, 1–22 (1961). Google Scholar  * DeWitt, E. J., Ramp, F. L. & Trapasso, L. E. Homogeneous hydrogenation catalyzed by boranes. _J. Am. Chem. Soc._ 83, 4672

(1961). CAS  Google Scholar  * Ramp, F. L., DeWitt, E. J. & Trapasso, L. E. Homogeneous hydrogenation catalyzed by boranes. _J. Org. Chem._ 27, 4368–4372 (1962). CAS  Google Scholar  *

Yalpani, M. & Köster, R. Partial hydrogenation: from anthracene to coronene. _Chem. Ber._ 123, 719–724 (1990). CAS  Google Scholar  * Köster, R., Schüßler, W. & Yalpani, M. Reduktion

kondensierter Arene mitBH-Boranen, I Reaktionen von Naphthalin, Anthracen und Phenanthren mit Tetraalkyldiboranen (6). _Chem. Ber._ 122, 677–686 (1989). Google Scholar  * Yalpani, M.,

Lunow, T. & Köster, R. Reduction of polycyclic arenes by-boranes, II. Borane catalyzed hydrogenation of naphthalenes to tetralins. _Chem. Ber._ 122, 687–693 (1989). CAS  Google Scholar 

* Haenel, M. W., Narangerel, J., Richter, U-B. & Rufińska, A. The first liquefaction of high-rank bituminous coals by preceding hydrogenation with homogeneous borane or iodine catalysts.

_Angew. Chem._ 45, 1061–1066 (2006). CAS  Google Scholar  * Siau, W-Y., Zhang, Y. & Zhao, Y. Stereoselective synthesis of _Z_-alkenes. _Top. Curr. Chem._ 327, 33–58 (2012). CAS  PubMed

  Google Scholar  * Jain, S. C. et al. Polyene pheromone components from an arctiid moth (_Utetheisa ornatrix_): characterization and synthesis. _J. Org. Chem._ 48, 2266–2270 (1983). CAS 

Google Scholar  * Fürstner, A., Guth, O., Rumbo, A. & Seidel, G. Ring closing alkyne metathesis. Comparative investigation of two different catalyst systems and application to the

stereoselective synthesis of olfactory lactones, azamacrolides, and the macrocyclic perimeter of the marine alkaloid nakadomarin A. _J. Am. Chem. Soc._ 121, 11108–11113 (1999). Google

Scholar  * Ghosh, A. K., Wang, Y. & Kim, J. T. Total synthesis of microtubule-stabilizing agent (−)-laulimalide. _J. Org. Chem._ 66, 8973–8982 (2001). CAS  PubMed  Google Scholar  *

Fürstner, A. & Davies, P. W. Alkyne metathesis. _Chem. Commun._ 2307–2320 (2005). * Caggiano, T. J., Siegel, S., King, A. O. & Shinkai, I. _Encyclopedia of Reagents for Organic

Synthesis_ Vol. 6 (ed. Paquette, L. A.) 3694–3869; 3861–3865; 3966–3867 (Wiley, 1995). Google Scholar  * Schrock, R. R. & Osborn, J. A. Catalytic hydrogenation using cationic rhodium

complexes. II. The selective hydrogenation of alkynes to _cis_ olefins. _J. Am. Chem. Soc._ 98, 2143–2147 (1976). CAS  Google Scholar  * Sodeoka, M. & Shibasaki, M. New functions of

(arene)tricarbonylchromium(0) complexes as hydrogenation catalysts: stereospecific semihydrogenation of alkynes and highly chemoselective hydrogenation of αβ-unsaturated carbonyl compounds.

_J. Org. Chem._ 50, 1147–1149 (1985). CAS  Google Scholar  * Van Laren, M. W. & Elsevier, C. J. Selective homogeneous palladium(0)-catalyzed hydrogenation of alkynes to (_Z_)-alkenes.

_Angew. Chem. Int. Ed._ 38, 3715–3717 (1999). CAS  Google Scholar  * Radkowski, K., Sundararaju, B. & Fürstner, A. A functional-group-tolerant catalytic _trans_ hydrogenation of alkynes.

_Angew. Chem. Int. Ed._ 52, 355–360 (2013). CAS  Google Scholar  * Parks, D. J., von H. Spence, R. E. & Piers, W. E. Bis(pentafluorophenyl)borane: synthesis, properties, and

hydroboration chemistry of a highly electrophilic borane reagent. _Angew. Chem. Int. Ed._ 34, 809–811 (1995). CAS  Google Scholar  * Parks, D. J., Piers, W. E. & Yap, G. P. A. Synthesis,

properties, and hydroboration activity of the highly electrophilic borane bis(pentafluorophenyl)borane, HB(C6F5)2 . _Organometallics_ 17, 5492–5503 (1998). CAS  Google Scholar  * Parks, D.

& Piers, W. Hydroboration of vinyl silanes with bis-(pentafluoro phenyl)borane: ground state β-silicon effects. _Tetrahedron_ 54, 15469–15488 (1998). CAS  Google Scholar  * Jiang, C.,

Blacque, O. & Berke, H. Metal-free hydrogen activation by the frustrated Lewis pairs of ClB(C6F5)2 and HB(C6F5)2 and bulky Lewis bases. _Organometallics_ 28, 5233–5239 (2009). CAS 

Google Scholar  * Jiang, C., Blacque, O., Fox, T. & Berke, H. Reversible, metal-free hydrogen activation by frustrated Lewis pairs. _Dalton Trans._ 40, 1091–1097 (2011). PubMed  Google

Scholar  * Chernichenko, K., Nieger, M., Leskelä, M. & Repo, T. Hydrogen activation by 2-boryl-_N_,_N_-dialkylanilines: a revision of Piers' ansa-aminoborane. _Dalton Trans._ 41,

9029–9032 (2012). CAS  PubMed  Google Scholar  * Chase, P. A. & Stephan, D. W. Hydrogen and amine activation by a frustrated Lewis pair of a bulky _N_-heterocyclic carbene and B(C6F5)3 .

_Angew. Chem. Int. Ed._ 47, 7433–7437 (2008). CAS  Google Scholar  * Robertson, A. P. M. et al. Experimental and theoretical studies of the potential interconversion of the amine-borane

_i_Pr2NH·BH(C6F5)2 and the aminoborane _i_Pr2N=B(C6F5)2 involving hydrogen loss and uptake. _Eur. J. Inorg. Chem._ 2011, 5279–5287 (2011). CAS  Google Scholar  * Erdmann, M. et al.

Functional group chemistry at intramolecular frustrated Lewis pairs: substituent exchange at the Lewis acid site with 9-BBN. _Dalton Trans._ 42, 709–718, (2013). CAS  PubMed  Google Scholar

  * Brown, H. C. _Hydroboration_ (W. A. Benjamin, 1962). Google Scholar  * Rokob, T. A., Hamza, A. & Pápai, I. Rationalizing the reactivity of frustrated Lewis pairs: thermodynamics of

H2 activation and the role of acid–base properties. _J. Am. Chem. Soc._ 131, 10701–10710 (2009). CAS  PubMed  Google Scholar  * Dureen, M. A., Brown, C. C. & Stephan, D. W. Deprotonation

and addition reactions of frustrated Lewis pairs with alkynes. _Organometallics_ 29, 6594–6607 (2010). CAS  Google Scholar  * Dureen, M. A. & Stephan, D. W. Terminal alkyne activation

by frustrated and classical Lewis acid/phosphine pairs. _J. Am. Chem. Soc._ 131, 8396–8397 (2009). CAS  PubMed  Google Scholar  * Jiang, C., Blacque, O. & Berke, H. Activation of

terminal alkynes by frustrated Lewis pairs. _Organometallics_ 29, 125–133 (2010). CAS  Google Scholar  * Moemming, C. M. et al. Formation of cyclic allenes and cumulenes by cooperative

addition of frustrated Lewis pairs to conjugated enynes and diynes. _Angew. Chem. Int. Ed._ 49, 2414–2417 (2010). CAS  Google Scholar  * Voss, T. et al. Frustrated Lewis pair behavior of

intermolecular amine/B(C6F5)3 pairs. _Organometallics_ 31, 2367–2378 (2012). CAS  Google Scholar  * Winkelhaus, D., Neumann, B., Stammler, H-G. & Mitzel, N. W. Intramolecular Lewis

acid–base pairs based on 4-ethynyl-2,6-lutidine. _Dalton Trans._ 41, 9143–9150 (2012). CAS  PubMed  Google Scholar  * Sumerin, V. et al. Amine-borane mediated metal-free hydrogen activation

and catalytic hydrogenation. _Top. Curr. Chem._ 332, 111–155 (2013). CAS  PubMed  Google Scholar  * Chai, J-D. & Head-Gordon, M. Long-range corrected hybrid density functionals with

damped atom–atom dispersion corrections. _Phys. Chem. Chem. Phys._ 10, 6615–6620 (2008). CAS  Google Scholar  Download references ACKNOWLEDGEMENTS The authors acknowledge financial support

from the Academy of Finland (139550) and the Hungarian Research Foundation (OTKA, grant K-81927) and COST action CM0905 (Organocatalysis). The authors also thank A. Reznichenko for

discussions and corrections during the preparation of the manuscript, M. Lindqvist for corrections and S. Heikkinen for help with NMR measurements. AUTHOR INFORMATION AUTHORS AND

AFFILIATIONS * Department of Chemistry, Laboratory of Inorganic Chemistry, University of Helsinki, PO Box 55, FIN-00014, Finland Konstantin Chernichenko, Martin Nieger, Markku Leskelä & 

Timo Repo * Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, PO Box 17, H-1525, Budapest, Hungary Ádám Madarász & Imre Pápai Authors *

Konstantin Chernichenko View author publications You can also search for this author inPubMed Google Scholar * Ádám Madarász View author publications You can also search for this author

inPubMed Google Scholar * Imre Pápai View author publications You can also search for this author inPubMed Google Scholar * Martin Nieger View author publications You can also search for

this author inPubMed Google Scholar * Markku Leskelä View author publications You can also search for this author inPubMed Google Scholar * Timo Repo View author publications You can also

search for this author inPubMed Google Scholar CONTRIBUTIONS K.C. and T.R. conceived and K.C. carried out the experiments. A.M. and I.P. designed and performed the DFT studies. All authors

discussed and co-wrote the paper. CORRESPONDING AUTHORS Correspondence to Imre Pápai or Timo Repo. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing financial

interests. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary information (PDF 6215 kb) RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE

Chernichenko, K., Madarász, Á., Pápai, I. _et al._ A frustrated-Lewis-pair approach to catalytic reduction of alkynes to _cis_-alkenes. _Nature Chem_ 5, 718–723 (2013).

https://doi.org/10.1038/nchem.1693 Download citation * Received: 22 February 2013 * Accepted: 13 May 2013 * Published: 07 July 2013 * Issue Date: August 2013 * DOI:

https://doi.org/10.1038/nchem.1693 SHARE THIS ARTICLE Anyone you share the following link with will be able to read this content: Get shareable link Sorry, a shareable link is not currently

available for this article. Copy to clipboard Provided by the Springer Nature SharedIt content-sharing initiative