Copper-Catalyzed Hydrofunctionalization of Alkynes

Alison M. Suess; Gojko Lalic

doi:10.1055/s-0035-1561357

Synlett, Table of Contents

Synlett 2016; 27(08): 1165-1174
DOI: 10.1055/s-0035-1561357

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Copper-Catalyzed Hydrofunctionalization of Alkynes

Authors

Alison M. Suess

Department of Chemistry, University of Washington, Seattle, Washington 98105, USA Email: lalic@chem.washington.edu
Gojko Lalic*

Department of Chemistry, University of Washington, Seattle, Washington 98105, USA Email: lalic@chem.washington.edu

Abstract

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Abstract

We have developed a general approach to the catalytic hydrofunctionalization of alkynes, involving hydrocupration and electrophilic functionalization of the resulting alkenylcopper intermediate. Using this approach with different electrophiles we have developed three transformations: semireduction, hydrobromination, and hydroalkylation of alkynes. In the context of a brief history of copper hydride complexes in organic chemistry, in this account we describe the key developments that inspired and enabled our research. We also describe the reaction development, the scope, and the mechanism of these transformations. In the process, we highlight some of the challenges inherent to our approach and summarize new insights that allowed us to successfully address them.

1 Introduction

2 Semireduction

3 Hydrobromination

4 Hydroalkylation

5 Conclusions

Key words

catalysis - copper - metal hydrides - N-heterocyclic carbenes - electrophiles

Full Text

References

References
1 Wurtz A. Ann. Chim. Phys. 1844; 11: 250

2a Mahoney WS, Brestensky DM, Stryker JM. J. Am. Chem. Soc. 1988; 110: 291
2b Brestensky DM, Huseland DE, McGettigan C, Stryker JM. Tetrahedron Lett. 1988; 29: 3749
2c Brestensky DM, Stryker JM. Tetrahedron Lett. 1989; 30: 5677
2d Koenig TM, Daeuble JF, Brestensky DM, Stryker JM. Tetrahedron Lett. 1990; 31: 3237

3 Churchill MR, Bezman SA, Osborn JA, Wormald J. J. Am. Chem. Soc. 1971; 93: 2063
4 Mahoney WS, Stryker JM. J. Am. Chem. Soc. 1989; 111: 8818
5 Brunner H, Miehling W. J. Organomet. Chem. 1984; 275: c17
6 Mori A, Fujita A, Nishihara Y, Hiyama T. Chem. Commun. (Cambridge) 1997; 2159
7 Ito H, Ishizuka T, Arimoto K, Miura K, Hosomi A. Tetrahedron Lett. 1997; 38: 8887
8 Lipshutz BH, Keith J, Papa P, Vivian R. Tetrahedron Lett. 1998; 39: 4627

9a Rendler S, Oestreich M. Angew. Chem. Int. Ed. 2007; 46: 498
9b Deutsch C, Krause N, Lipshutz BH. Chem. Rev. 2008; 108: 2916
9c Lipshutz BH. Synlett 2009; 509

10a Chiu P, Szeto C.-P, Geng Z, Cheng K.-F. Org. Lett. 2001; 3: 1901
10b Yun J, Buchwald SL. Org. Lett. 2001; 3: 1129
10c Lipshutz BH, Papa P. Angew. Chem. Int. Ed. 2002; 114: 4762
10d Chiu P, Leung SK. Chem. Commun. (Cambridge) 2004; 2308
10e Chae J, Yun J, Buchwald SL. Org. Lett. 2004; 6: 4809
10f Lam HW, Joensuu PM. Org. Lett. 2005; 7: 4225
10g Deschamp J, Chuzel O, Hannedouche J, Riant O. Angew. Chem. Int. Ed. 2006; 118: 1314
10h Chuzel O, Deschamp J, Chausteur C, Riant O. Org. Lett. 2006; 8: 5943
10i Welle A, Díez-González S, Tinant B, Nolan SP, Riant O. Org. Lett. 2006; 8: 6059
10j Zhao D, Oisaki K, Kanai M, Shibasaki M. Tetrahedron Lett. 2006; 47: 1403

11 Fujihara T, Xu T, Semba K, Terao J, Tsuji Y. Angew. Chem. Int. Ed. 2011; 50: 523
12 Fujihara T, Semba K, Terao J, Tsuji Y. Catal. Sci. Technol. 2014; 4: 1699
13 Mankad NP, Laitar DS, Sadighi JP. Organometallics 2004; 23: 3369
14 Whittaker AM, Lalic G. Org. Lett. 2013; 15: 1112
15 Uehling MR, Rucker RP, Lalic G. J. Am. Chem. Soc. 2014; 136: 8799

16a Uehling MR, Suess AM, Lalic G. J. Am. Chem. Soc. 2015; 137: 1424
16b Suess AM, Uehling MR, Kaminsky W, Lalic G. J. Am. Chem. Soc. 2015; 137: 7747

17 See also: Semba K, Fujihara T, Xu T, Terao J, Tsuji Y. Adv. Synth. Catal. 2012; 354: 1542

For selected examples, see:

18a Oblinger E, Montgomery J. J. Am. Chem. Soc. 1997; 119: 9065
18b Wang C.-C, Lin P.-S, Cheng C.-H. J. Am. Chem. Soc. 2002; 124: 9696
18c Takai K, Sakamoto S, Isshiki T. Org. Lett. 2003; 5: 653
18d Miller KM, Huang W.-S, Jamison TF. J. Am. Chem. Soc. 2003; 125: 3442
18e Mahandru GM, Liu G, Montgomery J. J. Am. Chem. Soc. 2004; 126: 3698
18f Ngai M.-Y, Barchuk A, Krische MJ. J. Am. Chem. Soc. 2006; 129: 280
18g Herath A, Thompson BB, Montgomery J. J. Am. Chem. Soc. 2007; 129: 8712
18h Patman RL, Chaulagain MR, Williams VM, Krische MJ. J. Am. Chem. Soc. 2009; 131: 2066
18i Nakao Y, Idei H, Kanyiva KS, Hiyama T. J. Am. Chem. Soc. 2009; 131: 5070
18j Malik HA, Sormunen GJ, Montgomery J. J. Am. Chem. Soc. 2010; 132: 6304
18k Zhou C.-Y, Zhu S.-F, Wang L.-X, Zhou Q.-L. J. Am. Chem. Soc. 2010; 132: 10955
18l Leung JC, Patman RL, Sam B, Krische MJ. Chem. Eur. J. 2011; 17: 12437
18m Wei C.-H, Mannathan S, Cheng C.-H. J. Am. Chem. Soc. 2011; 133: 6942
18n McInturff EL, Nguyen KD, Krische MJ. Angew. Chem. Int. Ed. 2014; 53: 3232
18o Nakai K, Yoshida Y, Kurahashi T, Matsubara S. J. Am. Chem. Soc. 2014; 136: 7797

19a Molinaro C, Jamison TF. J. Am. Chem. Soc. 2003; 125: 8076
19b Beaver MG, Jamison TF. Org. Lett. 2011; 13: 4140

20 Dang H, Cox N, Lalic G. Angew. Chem. Int. Ed. 2014; 53: 752
21 Dang H, Mailig M, Lalic G. Angew. Chem. Int. Ed. 2014; 53: 6473

22a Wyss CM, Tate BK, Bacsa J, Gray TG, Sadighi JP. Angew. Chem. Int. Ed. 2013; 52: 12920
22b Wyss CM, Tate BK, Bacsa J, Wieliczko M, Sadighi JP. Polyhedron 2014; 84: 87