Synthesis 2019; 51(06): 1329-1341
DOI: 10.1055/s-0037-1611704
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© Georg Thieme Verlag Stuttgart · New York

Zinc-Mediated Double Addition on Functionalized Nitriles

Julien Caillé
,
Mathilde Pantin
,
Fabien Boeda
,
Morwenna S. M. Pearson-Long*
Institut des Molécules et Matériaux du Mans (IMMM), UMR 6283 CNRS - Le Mans Université, Avenue Olivier Messiaen, 72085 Le Mans CEDEX 9, France   Email: Morwenna.pearson@univ-lemans.fr   Email: Philippe.bertus@univ-lemans.fr
,
Institut des Molécules et Matériaux du Mans (IMMM), UMR 6283 CNRS - Le Mans Université, Avenue Olivier Messiaen, 72085 Le Mans CEDEX 9, France   Email: Morwenna.pearson@univ-lemans.fr   Email: Philippe.bertus@univ-lemans.fr
› Author Affiliations
J. Caillé gratefully thanks the ‘Ministère de l’enseignement supérieur et de la recherche’ for a Ph.D. fellowship. M. Pantin thanks the ‘Université Bretagne Loire’ for a postdoctoral grant.
Further Information

Publication History

Received: 29 October 2018

Accepted after revision: 26 November 2018

Publication Date:
24 January 2019 (eFirst)

Abstract

Allylzinc reagents were used to access highly functionalized tertiary carbinamine derivatives in high yields from cyanoesters and cyanocarbonates. While the monoaddition of organometallics on nitriles is generally observed, in this work the nucleophilic allylation occurs twice, due to an intermediate transfer of the carbonyl moiety onto the nitrogen atom. The chemoselectivity of the reaction allows the presence of various functionalities and in the case of carbonate derivatives, the nature of the final product was modulated by kinetic control, giving selectively hydroxyamides or cyclic carbamates.

Supporting Information

 
  • References

  • 1 Hager A, Vrielink N, Hager D, Lefranc J, Trauner D. Nat. Prod. Rep. 2016; 33: 491

    • See for example:
    • 2a Guérinot A, Reymond S, Cossy J. Eur. J. Org. Chem. 2012; 19
    • 2b Jiang D, He T, Ma L, Wang Z. RSC Adv. 2014; 4: 64936

      See for instance:
    • 3a Fu Y, Hammarström LG. J, Miller TJ, Fronczek FR, McLaughlin ML, Hammer RP. J. Org. Chem. 2001; 66: 7118
    • 3b Ornelas C, Pennell R, Liebes LF, Weck M. Org. Lett. 2011; 13: 976
    • 3c Khan IU, Kattela S, Hassan A, Correira CR. D. Org. Biomol. Chem. 2016; 14: 9476

      See for instance:
    • 4a Cogan DA, Ellman JA. J. Am. Chem. Soc. 1999; 121: 268
    • 4b Fu P, Snapper ML, Hoveyda AH. J. Am. Chem. Soc. 2008; 130: 5530
    • 4c Kamau MG, Harikrishnan LS, Finlay HJ, Qiao JX, Jiang J, Poss MA, Salvati ME, Wexler RR, Lawrence RM. Tetrahedron 2012; 68: 2696
    • 4d Kano T, Kobayashi R, Maruoka K. Org. Lett. 2016; 18: 276
  • 5 Pearson-Long MS. M, Boeda F, Bertus P. Adv. Synth. Catal. 2017; 359: 179
  • 6 Clayden J, Greeves N, Warren S, Wothers P. Organic Chemistry . Oxford University Press; Oxford: 2001
    • 7a Savarin CG, Boice GN, Murry JA, Corley E, DiMichele L, Hughes D. Org. Lett. 2006; 8: 3903
    • 7b Mateos C, Rincón JA, Villanueva J. Tetrahedron Lett. 2013; 54: 2226
  • 8 Allen BB, Henze HR. J. Am. Chem. Soc. 1939; 61: 1790
    • 9a Alvernhe G, Laurent A. Tetrahedron Lett. 1973; 1057
    • 9b Gauthier R, Axiotis GP, Chastrette M. J. Organomet. Chem. 1977; 140: 245
    • 9c Kamau MG, Harikrishnan LS, Finlay HJ, Qiao JX, Jiang J, Poss MA, Salvati ME, Wexler RR, Lawrence RM. Tetrahedron 2012; 68: 2696
    • 10a Ciganek E. J. Org. Chem. 1992; 57: 4521
    • 10b Charette AB, Gagnon A, Janes M, Mellon C. Tetrahedron Lett. 1998; 39: 5147
    • 10c Charette AB, Mellon C. Tetrahedron 1998; 54: 10525
    • 10d Roth T, Wadepohl H, Clot E, Gade LH. Chem. Eur. J. 2015; 21: 18730
    • 11a Kuznetsov NY, Kolomnikova GD, Khrustalev VN, Golovanov DG, Bubnov YN. Eur. J. Org. Chem. 2008; 5647
    • 11b Kuznetsov NY, Maleev VI, Khrustalev VN, Mkrtchyan AF, Godovikov IA, Strelkova TV, Bubnov YN. Eur. J. Org. Chem. 2012; 334
    • 11c Ramadhar TR, Bansagi J, Batey RA. J. Org. Chem. 2013; 78: 1216
  • 12 Yu M, Zhang Y, Guo H. Synth. Commun. 1997; 27: 1495
    • 13a Jin S.-J, Araki S, Butsugan Y. Bull. Chem. Soc. Jpn. 1993; 66: 1528
    • 13b Ritson DJ, Cox RJ, Berge J. Org. Biomol. Chem. 2004; 2: 1921
    • 13c Yamamoto Y, Fujiwara N. Tetrahedron Lett. 1998; 39: 4729
    • 13d Kim SH, Lee HS, Kim KH, Kim JN. Tetrahedron Lett. 2009; 50: 1696
    • 13e Kim SH, Kim SH, Kim KH, Kim JN. Tetrahedron Lett. 2010; 51: 860
    • 13f Kim SH, Kim SH, Kim TH, Kim JN. Tetrahedron Lett. 2010; 51: 2774
    • 13g Kim SH, Kim YM, Kim JN. Bull. Korean Chem. Soc. 2010; 31: 2351
    • 13h Kim SH, Kim YM, Park BR, Kim JN. Bull. Korean Chem. Soc. 2010; 31: 3031
  • 14 Boukattaya F, Stanovych A, Setzer P, Abid S, Ammar H, Pearson-Long MS. M, Bertus P. Chem. Commun. 2012; 48: 8655
  • 15 Boukattaya F, Caillé J, Ammar H, Rouzier F, Boeda F, Pearson-Long MS. M, Bertus P. Synthesis 2016; 48: 906

    • See for instance:
    • 16a Bouchoule C, Miginiac P. C. R. Acad. Sci. Ser. C 1968; 266: 1614
    • 16b Rousseau G, Conia JM. Tetrahedron Lett. 1981; 22: 649
    • 16c Rousseau G, Drouin J. Tetrahedron 1983; 39: 2307
    • 16d McNulty J, McLeod D, Jenkins HA. Eur. J. Org. Chem. 2016; 688

      In some cases, nitriles remain unaffected in reactions involving allylzinc derivatives:
    • 17a Saidi MR, Azizi N. Tetrahedron: Asymmetry 2002; 13: 2523
    • 17b Ren H, Dunet G, Mayer P, Knochel P. J. Am. Chem. Soc. 2007; 129: 5376
    • 17c Chen Y.-H, Ellwart M, Malakhov V, Knochel P. Synthesis 2017; 49: 3215
    • 18a Mecozzi T, Petrini M. J. Org. Chem. 1999; 64: 8970
    • 18b Petrini M, Profera R, Righi P. J. Org. Chem. 2002; 67: 4530
    • 18c Zhang J, Wei C, Li C.-J. Tetrahedron Lett. 2002; 43: 5731
    • 19a Gaudemar M. C. R. Acad. Sci. Ser. C 1971; 273: 1669
    • 19b Knochel P, Normant JF. Tetrahedron Lett. 1986; 27: 1039
    • 19c Sklute G, Cavender H, Marek I. Org. React. 2015; 87: 507
  • 20 A mixture of α- and γ-addition products was obtained, probably due to steric reasons.
  • 21 El Alami N, Belaud C, Villieras J. J. Organomet. Chem. 1987; 319: 303
  • 22 Love BE, Jones EJ. J. Org. Chem. 1999; 64: 3755
  • 23 Setzer P, Forcher G, Boeda F, Pearson-Long MS. M, Bertus P. Eur. J. Org. Chem. 2014; 171
  • 24 Shen R, Lin CT, Bowman EJ, Bowman BJ, Porco JA. Jr. J. Am. Chem. Soc. 2003; 125: 7889
  • 25 Okimoto M, Chiba T. Synthesis 1996; 1188
  • 26 Davis OC. M. J. Chem . Soc. 1910; 97: 949
  • 27 Laroche C, Harakat D, Bertus P, Szymoniak J. Org. Biomol. Chem. 2005; 3: 3482
  • 28 Nakai K, Kurahashi T, Matsubara S. J. Am. Chem. Soc. 2011; 133: 11066
  • 29 Pearson-Long MS. M, Beauseigneur A, Karoyan P, Szymoniak J, Bertus P. Synthesis 2010; 3410
  • 30 Nolla-Saltiel R, Carrillo-Arcos UA, Porcel S. Synthesis 2014; 46: 165
  • 31 Wager J, Grošelj U, Meden A, Svete J, Stanovnik B. Tetrahedron 2008; 64: 2801
  • 32 Bose DS, Narsaiah AV. Synthesis 2001; 373
  • 33 Sattely ES, Cortez GA, Moebius DC, Shrock RR, Hoveyda AH. J. Am. Chem. Soc. 2005; 127: 8526