Synthesis of Chiral C1-Symmetric N-Heterocyclic Carbene Ligands: Application toward Copper-Catalyzed Homocoupling of 2-Naphthols

Michael Holtz-Mulholland; Shawn K. Collins

doi:10.1055/s-0033-1338564

Synthesis, Table of Contents

Synthesis 2014; 46(03): 375-380
DOI: 10.1055/s-0033-1338564

paper

Synthesis of Chiral C ₁-Symmetric N-Heterocyclic Carbene Ligands: Application toward Copper-Catalyzed Homocoupling of 2-Naphthols

Michael Holtz-Mulholland

Département de Chimie, Centre for Green Chemistry and Catalysis, Université de Montréal, CP 6128 Station Downtown, Montréal, QC, H3C 3J7, Canada Fax: +1(514)3437586 Email: shawn.collins@umontreal.ca

,

Shawn K. Collins*

Département de Chimie, Centre for Green Chemistry and Catalysis, Université de Montréal, CP 6128 Station Downtown, Montréal, QC, H3C 3J7, Canada Fax: +1(514)3437586 Email: shawn.collins@umontreal.ca

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Abstract

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Abstract

Novel chiral C ₁-symmetric NHC ligands can be prepared via dialkylation of chiral imidazoline scaffolds. Asymmetry in the ligand/metal complexes results from a chiral relay effect. The C ₁-symmetric nature of the NHC ligand was proposed to allow for improved reactivity versus other achiral and chiral NHC complexes. The benefit of such ligands was demonstrated in copper-catalyzed oxidative coupling reactions.

Key words

oxidative coupling - binaphthols - N-heterocyclic carbenes - copper - catalysis

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References

References

1a Cazin CS. J. Dalton Trans. 2013; 42: 7254
1b Egbert JD, Cazin CS. J, Nolan SP. Catal. Sci. Technol. 2013; 3: 912
1c Izquierdo J, Hutson GE, Cohen DT, Scheidt KA. Angew. Chem. Int. Ed. 2012; 51: 11686

2a Kundig EP, Jia Y, Katayev D, Nakanishi M. Pure Appl. Chem. 2012; 84: 1741
2b Wang F, Liu L.-j, Wang W, Li S, Shi M. Coord. Chem. Rev. 2012; 256: 804

3a Vieira EM, Snapper ML, Hoveyda AH. J. Am. Chem. Soc. 2011; 133: 3332
3b Lee K.-S, Hoveyda AH. J. Org. Chem. 2009; 74: 4455

4a Jung B, Hoveyda AH. J. Am. Chem. Soc. 2012; 134: 1490
4b Gao F, McGrath KP, Lee Y, Hoveyda AH. J. Am. Chem. Soc. 2010; 132: 14315
4c Grassi D, Alexakis A. Org. Lett. 2012; 14: 1568
4d Martin D, Kehrli S, d’Augustin M, Clavier H, Mauduit M, Alexakis A. J. Am. Chem. Soc. 2006; 128: 8416
4e Schneider N, César V, Bellemin-Laponnaz S, Gade LH. Organometallics 2005; 24: 4886

For a demonstrative example of the use of C ₂-symmetric vs C ₁-symmetric ligands in the asymmetric synthesis of aziridines see:

5a Hodgson DM, Hughes SP, Thompson AL, Heightman TD. Org. Lett. 2008; 10: 3453
5b Evans DA, Faul MM, Bilodeau MT, Anderson BA, Barnes DM. J. Am. Chem. Soc. 1993; 115: 5328
5c Evans DA, Bilodeau MT, Faul MM. J. Am. Chem. Soc. 1994; 116: 2742

For our own efforts in this area see:

6a Grandbois A, Mayer M.-E, Bédard M, Collins SK, Michel T. Chem. Eur. J. 2009; 15: 9655
6b Holtz-Mulholland M, de Léséleuc M, Collins SK. Chem. Commun. 2013; 49: 1835

7 Alexakis A, Mangeney P, Roland S. Synthesis 1999; 228

8a One of the first examples of the chiral relay strategy using NHC ligands was reported by Grubbs and co-workers: Seiders TJ, Ward DW, Grubbs RH. Org. Lett. 2001; 3: 3225
8b For additional references concerning theoretical calculations with regards to the function of chiral relays in catalysis see: Costabile C, Cavallo L. J. Am. Chem. Soc. 2004; 126: 9592

9a Stenne B, Timperio J, Savoie J, Dudding T, Collins SK. Org. Lett. 2010; 12: 2032
9b Savoie J, Stenne B, Collins SK. Adv. Synth. Catal. 2009; 351: 1826

10a Selim KB, Matsumoto Y, Yamada K.-i, Tomioka K. Angew. Chem. Int. Ed. 2009; 48: 8733
10b Selim KB, Nakanishi H, Matsumoto Y, Yamamoto Y, Yamada K.-i, Tomioka K. J. Org. Chem. 2011; 76: 1398

11 CCDC-913107 and CCDC-947160 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

12a Diez-Gonzalez S, Escudero-Adan EC, Benet-Buchholz J, Stevens ED, Slawin MZ. A, Nolan SP. Dalton Trans 2010; 39: 7595
12b Buried volumes were computed using the MoLNaC SambVca web application using a fixed bond length of 2 Å, a sphere radius of 3.5 Å, and scaled bond radii. For examples see: Poater A, Cosenza B, Correa A, Giudice S, Ragone F, Scarano V, Cavallo L. Eur. J. Inorg. Chem. 2009; 1759
12c For a comparison of buried volumes for an assortment of NHC complexes see: Clavier H, Nolan SP. Chem. Commun. 2010; 46: 841

For some early work into asymmetric oxidative coupling see:

13a Smrcina M, Polakova J, Vyskocil S, Kocovsky P. J. Org. Chem. 1993; 58: 4534
13b Nakajima M, Kanayama K, Miyoshi I, Hashimoto S. Tetrahedron Lett. 1995; 36: 9519
13c Nakajima M, Miyoshi I, Kanayama K, Hashimoto S.-I. J. Org. Chem. 1999; 64: 2264
13d Kim KH, Lee DW, Lee YS, Ko DH, Ha DC. Tetrahedron 2004; 60: 9037

For reviews of asymmetric catalysis with BINOL derivatives, see:

13e Brunel JM. Chem. Rev. 2005; 105: 857
13f Terada M. Chem. Commun. 2008; 4097

For catalysts possessing a chiral scaffold derived from oxidative homocoupling see:

13g Connon SJ. Angew. Chem. Int. Ed. 2006; 45: 3909
13h Akiyama T. Chem. Rev. 2007; 107: 5744

14a Li X, Yang J, Kozlowski MC. Org. Lett. 2001; 3: 1137
14b Li X, Hewgley JB, Mulrooney CA, Yang JM, Kozlowski MC. J. Org. Chem. 2003; 68: 5500
14c Xie X, Phuan PW, Kozlowski MC. Angew. Chem. Int. Ed. 2003; 42: 2168
14d Mulrooney CA, Li X, DiVirgilio ES, Kozlowski MC. J. Am. Chem. Soc. 2003; 125: 6856
14e DiVirgilio ES, Dugan EC, Mulrooney CA, Kozlowski MC. Org. Lett. 2007; 9: 385
14f Podlesny EE, Kozlowski MC. Org. Lett. 2012; 14: 1408
14g Morgan BJ, Mulrooney CA, O’Brien EM, Kozlowski MC. J. Org. Chem. 2010; 75: 30
14h Kozlowski MC, Morgan BJ, Linton EC. Chem. Soc. Rev. 2009; 38: 3193
14i Ashenhurst JA. Chem. Soc. Rev. 2010; 39: 540

Complexes based on vanadium have been increasingly studied:

15a Takizawa S, Katayama T, Kameyama C, Onitsuka K, Suzuki T, Yanagida T, Kawai T, Sasai H. Chem. Commun. 2008; 1810
15b Takizawa S, Katayama T, Sasai H. Chem. Commun. 2008; 4113

16a Yan P, Sugiyama Y, Takahashi Y, Kinemuchi H, Temma T, Habaue S. Tetrahedron 2008; 64: 4325
16b Habaue S, Temma T, Sugiyama Y, Yan P. Tetrahedron Lett. 2007; 48: 8595

17 For an example of the state of the art in heterocoupling see: Egami H, Matsumoto K, Oguma T, Kunisu T, Katsuki T. J. Am. Chem. Soc. 2010; 132: 13633

For reactions catalyzed by complexes of the type (NHC)CuX see:

18a Kaur H, Zinn FK, Stevens ED, Nolan SP. Organometallics 2004; 23: 1157
18b Welle A, Díez-González S, Tinant B, Nolan SP, Riant O. Org. Lett. 2006; 8: 6059
18c Munro-Leighton C, Blue ED, Gunnoe TB. J. Am. Chem. Soc. 2006; 128: 1446
18d Trost BM, Dong G. J. Am. Chem. Soc. 2006; 128: 6054
18e Fructos MR, Belderrain TR, Nicasio MC, Nolan SP, Kaur H, Díaz-Requejo MM, Pérez PJ. J. Am. Chem. Soc. 2004; 126: 10846
18f Lebel H, Davi M, Díez-González S, Nolan SP. J. Org. Chem. 2007; 72: 144
18g Díez-González S, Correa A, Cavallo L, Nolan SP. Chem. Eur. J. 2006; 12: 7558
18h Boogaerts II. F, Fortman GC, Furst MR. L, Cazin CS. J, Nolan SP. Angew. Chem. Int. Ed. 2010; 49: 8674

For examples in asymmetric catalysis see:

18i Grassi D, Dolka C, Jackowski O, Alexakis A. Chem. Eur. J. 2013; 19: 1466
18j Germain N, Magrez M, Kehrli S, Mauduit M, Alexakis A. Eur. J. Org. Chem. 2012; 5301

Supplementary Material

Supporting Information

Synthesis of Chiral C 1-Symmetric N-Heterocyclic Carbene Ligands: Application toward Copper-Catalyzed Homocoupling of 2-Naphthols

Synthesis of Chiral C ₁-Symmetric N-Heterocyclic Carbene Ligands: Application toward Copper-Catalyzed Homocoupling of 2-Naphthols