Organic Letters
Letter
Hydrosilylation of Unsymmetrical Alkynes Catalyzed by a Well-
Defined, Low-Valent Cobalt Catalyst. Org. Lett. 2016, 18, 4242−4245.
(e) Zuo, Z.; Yang, J.; Huang, Z. Cobalt-Catalyzed Alkyne Hydro-
silylation and Sequential Vinylsilane Hydroboration with Markovnikov
Selectivity. Angew. Chem., Int. Ed. 2016, 55, 10839−10843.
(f) Docherty, J. H.; Peng, J.; Dominey, A. P.; Thomas, S. P. Activation
and discovery of earth-abundant metal catalysts using sodium tert-
butoxide. Nat. Chem. 2017, 9, 595. (g) Du, X.; Hou, W.; Zhang, Y.;
Huang, Z. Pincer cobalt complex-catalyzed Z-selective hydrosilylation
of terminal alkynes. Org. Chem. Front. 2017, 4, 1517−1521. (h) Guo, J.;
Shen, X.; Lu, Z. Regio- and Enantioselective Cobalt-Catalyzed
Sequential Hydrosilylation/Hydrogenation of Terminal Alkynes.
Angew. Chem., Int. Ed. 2017, 56, 615−618. (i) Teo, W. J.; Wang, C.;
Tan, Y. W.; Ge, S. Cobalt-Catalyzed Z-Selective Hydrosilylation of
Terminal Alkynes. Angew. Chem., Int. Ed. 2017, 56, 4328−4332. (j) Wu,
C.; Teo, W. J.; Ge, S. Cobalt-Catalyzed (E)-Selective anti-Markovnikov
Hydrosilylation of Terminal Alkynes. ACS Catal. 2018, 8, 5896−5900.
(k) Wu, G.; Chakraborty, U.; Jacobi von Wangelin, A. Regiocontrol in
the cobalt-catalyzed hydrosilylation of alkynes. Chem. Commun. 2018,
54, 12322−12325. (l) Zhang, S.; Ibrahim, J. J.; Yang, Y. An NNN-
Pincer-Cobalt Complex Catalyzed Highly Markovnikov-Selective
Alkyne Hydrosilylation. Org. Lett. 2018, 20, 6265−6269. (m) Li, R.-
H.; An, X.-M.; Yang, Y.; Li, D.-C.; Hu, Z.-L.; Zhan, Z.-P. Highly Regio-
and Stereoselective Heterogeneous Hydrosilylation of Terminal
Alkynes over Cobalt-Metalated Porous Organic Polymer. Org. Lett.
2018, 20, 5023−5026.
AUTHOR INFORMATION
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Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the Ministry of Education of
Singapore (R-143-000-A07-112).
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REFERENCES
■
(1) (a) Blumenkopf, T. A.; Overman, L. E. Vinylsilane- and
Alkynylsilane-terminated Cyclization Reactions. Chem. Rev. 1986, 86,
857−873. (b) Fleming, I.; Barbero, A.; Walter, D. Stereochemical
Control in Organic Synthesis Using Silicon-Containing Compounds.
Chem. Rev. 1997, 97, 2063−2192. (c) Langkopf, E.; Schinzer, D. Uses
of Silicon-Containing Compounds in the Synthesis of Natural
Products. Chem. Rev. 1995, 95, 1375−1408.
(2) (a) Nicolaou, K. C.; Dai, W.-M.; Tsay, S.-C.; Estevez, V. A.;
Wrasidlo, W. Designed Enediynes: A New Class of DNA-Cleaving
Molecules with Potent and Selective Anticancer Activity. Science 1992,
256, 1172−1178. (b) Ma, X.; Banwell, M. G.; Willis, A. C.
Chemoenzymatic Total Synthesis of the Phytotoxic Geranylcyclohex-
entriol (−)-Phomentrioloxin. J. Nat. Prod. 2013, 76, 1514−1518.
(c) Trost, B. M.; Masters, J. T.; Le Vaillant, F.; Lumb, J.-P. Synthesis of a
1,3-Bridged Macrobicyclic Enyne via Chemoselective Cycloisomeriza-
tion Using Palladium-Catalyzed Alkyne−Alkyne Coupling. J. Org.
Chem. 2016, 81, 10023−10028. (d) Trost, B. M.; Masters, J. T.
Transition Metal-Catalyzed Couplings of Alkynes to 1,3-Enynes:
Modern Methods and Synthetic Applications. Chem. Soc. Rev. 2016, 45,
2212−2238.
(6) (a) Wang, C.; Teo, W. J.; Ge, S. Access to Stereodefined (Z)-
Allylsilanes and (Z)-Allylic Alcohols via Cobalt-Catalyzed Regiose-
lective Hydrosilylation of Allenes. Nat. Commun. 2017, 8, 2258.
(b) Wang, C.; Teo, W. J.; Ge, S. Cobalt-Catalyzed Regiodivergent
Hydrosilylation of Vinylarenes and Aliphatic Alkenes: Ligand- and
Silane-Dependent Regioselectivities. ACS Catal. 2017, 7, 855−863.
(c) Sang, H. L.; Yu, S.; Ge, S. Cobalt-catalyzed regioselective
stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated
dienes. Chem. Sci. 2018, 9, 973−978.
(7) 1,4-Diaryl-1,3-diynes can undergo double hydrosilylation
reactions with secondary hydrosilanes. See: Matsuda, T.; Kadowaki,
S.; Murakami, M. Ruthenium-Catalysed Double trans-Hydrosilylation
of 1,4-Diarylbuta-1,3-diynes Leading to 2,5-Diarylsiloles. Chem.
Commun. 2007, 2627−2629.
(3) (a) Kusumoto, T.; Ando, K.; Hiyama, T. Hydrosilylation of 1,4-
Bis(trimethylsilyl)butadiyne and Silyl-Substituted Butenynes. Bull.
Chem. Soc. Jpn. 1992, 65, 1280−1290. (b) Tillack, A.; Pulst, S.;
Baumann, W.; Baudisch, H.; Kortus, K.; Rosenthal, U. Hydrosilylierung
von Symmetrisch Disubstituierten Alkinen und Butadiinen mit
L2Ni(0)-Butadiin-Komplexen [L = Ph3P, (o-Tol-O)3P] als Katalysa-
toren. J. Organomet. Chem. 1997, 532, 117−123.
̈
(8) For a related example, see: Trost, B. M.; Ball, Z. T.; Joge, T. A
Chemoselective Reduction of Alkynes to (E)-Alkenes. J. Am. Chem. Soc.
2002, 124, 7922−7923.
(9) For a related example, see: Tamao, K.; Kumada, M.; Maeda, K.
Silafunctional compounds in organic synthesis. 21. Hydrogen peroxide
oxidation of alkenyl(alkoxy)silanes. Tetrahedron Lett. 1984, 25, 321−
324.
(4) (a) Kusumoto, T.; Hiyama, T. Hydrosilylation of 1,4-Bis-
(trimethylsilyl)-1,3-butadiyne. Chem. Lett. 1985, 14, 1405−1408.
(b) Tillack, A.; Michalik, D.; Koy, C.; Michalik, M. Catalytic
Asymmetric Hydrosilylation of Butadiynes: A New Aynthesis of
Optically Active Allenes. Tetrahedron Lett. 1999, 40, 6567−6568.
(c) Perry, R. J.; Karageorgis, M.; Hensler, J. Hydrosilylation Reactions
of 1,3-Diynes and Bis(silyl hydrides): Model Studies and Polymer-
izations. Macromolecules 2007, 40, 3929−3938. (d) Alonso, F.;
(10) For related examples, see: (a) Hirabayashi, K.; Kawashima, J.;
Nishihara, Y.; Mori, A.; Hiyama, T. A New Transformation of Silanols.
Palladium-Catalyzed Cross-Coupling with Organic Halides in the
Presence of Silver(I) Oxide. Org. Lett. 1999, 1, 299−302. (b) Denmark,
S. E.; Regens, C. S. Palladium-Catalyzed Cross-Coupling Reactions of
Organosilanols and Their Salts: Practical Alternatives to Boron- and
Tin-Based Methods. Acc. Chem. Res. 2008, 41, 1486−1499. (c) Den-
mark, S. E.; Ambrosi, A. Why You Really Should Consider Using
Palladium-Catalyzed Cross-Coupling of Silanols and Silanolates. Org.
Process Res. Dev. 2015, 19, 982−994.
(11) (a) Sun, J.; Deng, L. Cobalt Complex-Catalyzed Hydrosilylation
of Alkenes and Alkynes. ACS Catal. 2016, 6, 290−300. (b) Ai, W.;
Zhong, R.; Liu, X.; Liu, Q. Hydride Transfer Reactions Catalyzed by
Cobalt Complexes. Chem. Rev. 2019, 119, 2876−2953.
́
Buitrago, R.; Moglie, Y.; Sepulveda-Escribano, A.; Yus, M. Selective
Hydrosilylation of 1,3-Diynes Catalyzed by Titania-Supported
Platinum. Organometallics 2012, 31, 2336−2342. (e) Walkowiak, J.;
Salamon, K.; Franczyk, A.; Stefanowska, K.; Szyling, J.; Kownacki, I. Pt-
Catalyzed Hydrosilylation of 1,3-Diynes with Triorganosilanes: Regio-
and Stereoselective Synthesis of Mono- or Bis-silylated Adducts. J. Org.
Chem. 2019, 84, 2358−2365.
(5) For selected recent examples, see: (a) Huang, K.-H.; Isobe, M.
Highly Regioselective Hydrosilylation of Unsymmetric Alkynes Using a
Phenylthio Directing Group. Eur. J. Org. Chem. 2014, 2014, 4733−
4740. (b) Mo, Z.; Xiao, J.; Gao, Y.; Deng, L. Regio- and Stereoselective
Hydrosilylation of Alkynes Catalyzed by Three-Coordinate Cobalt(I)
Alkyl and Silyl Complexes. J. Am. Chem. Soc. 2014, 136, 17414−17417.
(c) Guo, J.; Lu, Z. Highly Chemo-, Regio-, and Stereoselective Cobalt-
Catalyzed Markovnikov Hydrosilylation of Alkynes. Angew. Chem., Int.
́
Ed. 2016, 55, 10835−10838. (d) Rivera-Hernandez, A.; Fallon, B. J.;
Ventre, S.; Simon, C.; Tremblay, M.-H.; Gontard, G.; Derat, E.;
Amatore, M.; Aubert, C.; Petit, M. Regio- and Stereoselective
D
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