Triazolylidene Ligands Allow Cobalt-Catalyzed C–H/C–O Alkenyl­ations at Ambient Temperature

Dedicated to Prof. Dr. Herbert Mayr

Abstract

Direct alkenylation through C–H/C–O cleavage was accomplished under mild reaction conditions by cobalt catalysts derived from novel triazolylidene ligands. The most effective ligand is characterized by sterically demanding substituents on the 1,4-N-atoms of the triazolylidene neighboring the carbene center. The C–H alkenylations proved viable with alkenyl acetates, carbamates, carbonates and phosphates. For acyclic electrophiles, diastereoconvergent C–O functionalizations were observed.

Key words

carbene - cobalt - C–H activation - C–O functionalization - triazolylidene

• References

• 1a Schmidt AW. Reddy KR. Knölker H.-J. Chem. Rev. 2012; 112: 3193
• 1b Kochanowska-Karamyan AJ. Hamann MT. Chem. Rev. 2010; 110: 4489
• 1c Fan H. Peng J. Hamann MT. Hu J.-F. Chem. Rev. 2008; 108: 264
• 1d Humphrey GR. Kuethe JT. Chem. Rev. 2006; 106: 2875
• 1e Ackermann L. Synlett 2007; 507

Selected reviews:
• 2a Grimsdale AC. Leok Chan K. Martin RE. Jokisz PG. Holmes AB. Chem. Rev. 2009; 109: 897
• 2b Murphy AR. Fréchet JM. J. Chem. Rev. 2007; 107: 1066
• 3a Song G. Li X. Acc. Chem. Res. 2015; 48: 1007
• 3b Shin K. Kim H. Chang S. Acc. Chem. Res. 2015; 48: 1040
• 3c Segawa Y. Maekawa T. Itami K. Angew. Chem. Int. Ed. 2015; 54: 66
• 3d Kuhl N. Schröder N. Glorius F. Adv. Synth. Catal. 2014; 356: 1443
• 3e Wencel-Delord J. Glorius F. Nat. Chem. 2013; 5: 369
• 3f Satoh T. Miura M. Chem. Eur. J. 2010; 16: 11212
• 3g Giri R. Shi B.-F. Engle KM. Maugel N. Yu J.-Q. Chem. Soc. Rev. 2009; 38: 3242
• 3h Chen X. Engle KM. Wang D.-H. Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094
• 3i Ackermann L. Vicente R. Kapdi AR. Angew. Chem. 2009; 121: 9976
• 4 Chirik P. Morris R. Acc. Chem. Res. 2015; 48: 2495

For representative reviews, see:
• 5a Misal CL. C. Naoto C. Chem. Lett. 2015; 44: 410
• 5b McCann SD. Stahl SS. Acc. Chem. Res. 2015; 48: 1756
• 5c Koji H. Masahiro M. Chem. Lett. 2015; 44: 868
• 5d Daugulis O. Roane J. Tran LD. Acc. Chem. Res. 2015; 48: 1053
• 6a Cera G. Ackermann L. Top. Curr. Chem. 2016; 374: 57
• 6b Sun C.-L. Li B.-J. Shi Z.-J. Chem. Rev. 2011; 111: 1293
• 6c Nakamura E. Yoshikai N. J. Org. Chem. 2010; 75: 6061
• 7a Liu W. Ackermann L. ACS Catal. 2016; 6: 3743
• 7b Wang C. Synlett 2013; 24: 1606
• 8a Moselage M. Li J. Ackermann L. ACS Catal. 2016; 6: 498
• 8b Yoshikai N. ChemCatChem 2015; 7: 732
• 8c Gao K. Yoshikai N. Acc. Chem. Res. 2014; 47: 1208
• 8d Ackermann L. J. Org. Chem. 2014; 79: 8948
• 9a Yamakawa T. Seto YW. Yoshikai N. Synlett 2015; 26: 340
• 9b Gao K. Yamakawa T. Yoshikai N. Synthesis 2014; 46: 2024
• 9c Gao K. Paira R. Yoshikai N. Adv. Synth. Catal. 2014; 356: 1486
• 9d Gao K. Yoshikai N. J. Am. Chem. Soc. 2013; 135: 9279
• 9e Gao K. Yoshikai N. Chem. Commun. 2012; 4305
• 9f Gao K. Lee P.-S. Long C. Yoshikai N. Org. Lett. 2012; 14: 4234
• 10a Mei R. Ackermann L. Adv. Synth. Catal. 2016; 358: 2443
• 10b Li J. Ackermann L. Chem. Eur. J. 2015; 21: 5718
• 10c Punji B. Song W. Shevchenko GA. Ackermann L. Chem. Eur. J. 2013; 19: 10605
• 10d Song W. Ackermann L. Angew. Chem. Int. Ed. 2012; 51: 8251

For selected examples, see:
• 11a Cong X. Zhai S. Zeng X. Org. Chem. Front. 2016; 3: 673
• 11b Chen Q. Ilies L. Yoshikai N. Nakamura E. Org. Lett. 2011; 13: 3232
• 11c Chen Q. Ilies L. Nakamura E. J. Am. Chem. Soc. 2011; 133: 428
• 11d Halbritter G. Knoch F. Wolski A. Kisch H. Angew. Chem., Int. Ed. Engl. 1994; 33: 1603

For reviews, see:
• 12a Flanigan DM. Romanov-Michailidis F. White NA. Rovis T. Chem. Rev. 2015; 115: 9307
• 12b Enders D. Niemeier O. Henseler A. Chem. Rev. 2007; 107: 5606
• 12c Enders D. Balensiefer T. Acc. Chem. Res. 2004; 37: 534
• 12d Enders D. Breuer K. Teles JH. Ebel K. J. Prakt. Chem. 1997; 339: 397

For representative examples, see:
• 13a Gawin R. Pieczykolan M. Malińska M. Woźniak K. Grela K. Synlett 2013; 24: 1250
• 13b Zhao L. Ma Y. Duan W. He F. Chen J. Song C. Org. Lett. 2012; 14: 5780
• 13c Strand RB. Helgerud T. Solvang T. Dolva A. Sperger CA. Fiksdahl A. Tetrahedron: Asymmetry 2012; 23: 1350
• 13d Loh CC. J. Enders D. Chem. Eur. J. 2012; 18: 10212
• 13e Bouffard J. Keitz BK. Tonner R. Guisado-Barrios G. Frenking G. Grubbs RH. Bertrand G. Organometallics 2011; 30: 2617
• 13f Trnka TM. Morgan JP. Sanford MS. Wilhelm TE. Scholl M. Choi T.-L. Ding S. Day MW. Grubbs RH. J. Am. Chem. Soc. 2003; 125: 2546
• 13g Enders D. Gielen H. J. Organomet. Chem. 2001; 617–618: 70
• 13h Enders D. Gielen H. Breuer K. Tetrahedron: Asymmetry 1997; 8: 3571

For reviews on C–O activation, see:
• 14a Cornella J. Zarate C. Martin R. Chem. Soc. Rev. 2014; 43: 8081
• 14b Kozhushkov SI. Potukuchi HK. Ackermann L. Cat. Sci. Tech. 2013; 3: 562
• 14c Rosen BM. Quasdorf KW. Wilson DA. Zhang N. Resmerita A.-M. Garg NK. Percec V. Chem. Rev. 2011; 111: 1346
• 14d Yu D.-G. Li B.-J. Shi Z.-J. Acc. Chem. Res. 2010; 43: 1486
• 15 Moselage M. Sauermann N. Richter SC. Ackermann L. Angew. Chem. Int. Ed. 2015; 54: 6352
• 16 Yatham VR. Harnying W. Kootz D. Neudörfl J.-M. Schlörer NE. Berkessel A. J. Am. Chem. Soc. 2016; 138: 2670
• 17 Under otherwise identical reaction conditions, N-methyl- and N-phenylindole did not lead to any C–H activation
• 18 Gensch T. Hopkinson MN. Glorius F. Wencel-Delord J. Chem. Soc. Rev. 2016; 45: 2900
• 19 Wagner JP. Schreiner PR. Angew. Chem. Int. Ed. 2015; 54: 12274
• 20 Enders D. Breuer K. Kallfass U. Balensiefer T. Synthesis 2003; 1292
• 21 Ackermann L. Lygin AV. Org. Lett. 2011; 13: 3332
• 22 Onishi Y. Yoneda Y. Nishimoto Y. Yasuda M. Baba A. Org. Lett. 2012; 14: 5788
• 23 Qin X. Liu H. Qin D. Wu Q. You J. Zhao D. Guo Q. Huang X. Lan J. Chem. Sci. 2013; 4: 1964
• 24 Ding Y. Wang W. Liu Z. Phosphorus, Sulfur Silicon Relat. Elem. 1996; 118: 113
• 25 Silvestri MG. Hanson MP. Pavlovich JG. Studen LF. DeClue MS. DeGraffenreid MR. Amos CD. J. Org. Chem. 1999; 64: 6597
• 26 Boultadakis-Arapinis M. Hopkinson MN. Glorius F. Org. Lett. 2014; 16: 1630
• 27 Narlawar R. Werry EL. Scarf AM. Hanani R. Chua SW. King VA. Barron ML. Martins RN. Ittner LM. Rendina LM. Kassiou M. J. Med. Chem. 2015; 58: 8743