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Synthesis 2019; 51(06): 1329-1341
DOI: 10.1055/s-0037-1611704
DOI: 10.1055/s-0037-1611704
feature
Zinc-Mediated Double Addition on Functionalized Nitriles
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.Weitere Informationen
Publikationsverlauf
Received: 29. Oktober 2018
Accepted after revision: 26. November 2018
Publikationsdatum:
24. Januar 2019 (online)
![](https://www.thieme-connect.de/media/synthesis/201906/lookinside/thumbnails/ss-2018-z0726-fa_10-1055_s-0037-1611704-1.jpg)
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.
Key words
allylation - nitriles - nucleophilic addition - organometallic reagents - tertiary carbinamines - zincSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611704.
- Supporting Information
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References
- 1 Hager A, Vrielink N, Hager D, Lefranc J, Trauner D. Nat. Prod. Rep. 2016; 33: 491
- 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
- 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
- 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
- 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
- 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
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In some cases, nitriles remain unaffected in reactions involving allylzinc derivatives: