Hydrogen-Bond-Promoted Metal-Free Hydroamination of Alkynes

Janet Bahri; Nour Tanbouza; Thierry Ollevier; Marc Taillefer; Florian Monnier

doi:10.1055/s-0039-1690988

Synlett, Inhaltsverzeichnis

Synlett 2019; 30(18): 2086-2090
DOI: 10.1055/s-0039-1690988

letter

Hydrogen-Bond-Promoted Metal-Free Hydroamination of Alkynes

Janet Bahri

^aÉcole Nationale Supérieure de Chimie de Montpellier, Institut Charles Gerhardt, CNRS UMR 5253, AM2N, 8 rue de l’école normale, 34296 Montpellier Cedex 05, France eMail: marc.taillefer@enscm.fr

,

Nour Tanbouza

^bDépartement de Chimie, 1045 avenue de la Médecine, Université Laval, Québec, QC, G1V 0A6, Canada eMail: thierry.ollevier@chm.ulaval.ca

,

Thierry Ollevier ∗

^bDépartement de Chimie, 1045 avenue de la Médecine, Université Laval, Québec, QC, G1V 0A6, Canada eMail: thierry.ollevier@chm.ulaval.ca

,

Marc Taillefer ∗

^aÉcole Nationale Supérieure de Chimie de Montpellier, Institut Charles Gerhardt, CNRS UMR 5253, AM2N, 8 rue de l’école normale, 34296 Montpellier Cedex 05, France eMail: marc.taillefer@enscm.fr

,

Florian Monnier ∗

^aÉcole Nationale Supérieure de Chimie de Montpellier, Institut Charles Gerhardt, CNRS UMR 5253, AM2N, 8 rue de l’école normale, 34296 Montpellier Cedex 05, France eMail: marc.taillefer@enscm.fr

^cIUF Institut Universitaire de France, 1 rue Descartes, 75231 Paris, France eMail: florian.monnier@enscm.fr

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Abstract

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Abstract

An original metal-free regio- and stereoselective intermolecular hydroamination of alkynes is described. Various (E)-enamines were obtained from arylacetylenes and aliphatic secondary amines in the presence of ethylene glycol as a solvent. The latter is assumed to play a major role in the mechanism through hydrogen bonding and proton exchange.

Key words

hydroamination - alkynes - amines - metal-free - enamines - green chemistry

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Referenzen

References and Notes

1a O’Hagan D. Nat. Prod. Rep. 2000; 17: 435
1b Liddell JR. Nat. Prod. Rep. 2002; 19: 773

2a Glisan King A, Meinwald J. Chem. Rev. 1996; 96: 1105
2b Mitchinson A, Nadin A. J. Chem. Soc., Perkin Trans. 1 2000; 1: 2862

3a Enamines: Synthesis Structure and Reactions, 2nd ed. Cook AG. Dekker; New York: 1988
3b Kuckländer U. In The Chemistry of Enamines, Part 1 . Rappoport Z. Wiley; Chichester: 1994: 523
3c Kobayashi S, Ishitani H. Chem. Rev. 1999; 99: 1069
3d Mukherjee S, Yang JW, Hoffmann S, List B. Chem. Rev. 2007; 107: 5471

For reviews on hydroamination, see:

4a Müller TE, Beller M. Chem. Rev. 1998; 98: 675
4b Alonso F, Beletskaya IP, Yus M. Chem. Rev. 2004; 104: 3079
4c Hartwig JF. Pure Appl. Chem. 2004; 76: 507
4d Chemler S. Org. Biomol. Chem. 2009; 7: 3009
4e Huang L, Arndt M, Gooßen K, Heydt H, Gooßen LJ. Chem. Rev. 2015; 115: 2596
4f Bernoud E, Lepori C, Mellah M, Schulz E, Hannedouche J. Catal. Sci. Technol. 2015; 5: 2017
4g Evano G, Gaumont A.-C, Alayrac C, Wrona IE, Giguere JR, Delacroix O, Bayle A, Jouvin K, Theunissen C, Gatignol J, Silvanus AC. Tetrahedron 2014; 70: 1529
4h Schafer LL, Yim JC. H, Yonson N. In Metal-Catalyzed Cross-Coupling Reactions and More . de Meijere A, Bräse S, Oestreich M. Wiley-VCH; Weinheim: 2014. Chap. 15, 1135

5a Hong S, Marks TJ. Acc. Chem. Res. 2004; 37: 673
5b Severin R, Doye S. Chem. Soc. Rev. 2007; 36: 1407
5c Gils RL, Sullivan JD, Steiner AM, Looper RE. Angew. Chem. Int. Ed. 2009; 48: 3116
5d Reznichenko AL, Hultzsch KC. Organometallics 2013; 32: 1394

6a Leitch DC, Turner CS, Shafer LL. Angew. Chem. Int. Ed. 2010; 49: 6382
6b Sarma R, Prajapati D. Chem. Commun. 2011; 47: 9525
6c Brinkmann C, Barrett AG. M, Hill MS, Procopiou PA. J. Am. Chem. Soc. 2012; 134: 2193
6d Liu B, Roisnel T, Carpentier JF, Sarazin Y. Chem. Eur. J. 2013; 19: 13445

7a Moran J, Cebrowski PH, Beauchemin AM. J. Org. Chem. 2008; 73: 1004
7b Rizk T, Bilodeau EJ. F, Beauchemin AM. Angew. Chem. Int. Ed. 2009; 48: 8325
7c Ackermann L, Kozhushkov SI, Yufit DS, Marek I. Synlett 2011; 1515
7d Fleisher S, Werkeister S, Zhou S, Junge K, Beller M. Chem. Eur. J. 2012; 18: 9005
7e Lin J.-S, Yu P, Huang L, Zhang P, Tan B, Liu X.-Y. Angew. Chem. Int. Ed. 2015; 54: 7847

8a Tzalis D, Koradin C, Knochel P. Tetrahedron Lett. 1999; 40: 6193
8b Rodriguez AL, Koradin C, Dohle W, Knochel P. Angew. Chem. Int. Ed. 2000; 39: 2488
8c Imahori T, Hori C, Kondo Y. Adv. Synth. Catal. 2004; 346: 1090
8d Alsabesh PG, Lundgren RJ, Longobardi LE, Stradiotto M. Chem. Commun. 2011; 47: 6936
8e Patel M, Saunthawal RK, Verma AK. Tetrahedron Lett. 2014; 55: 1310
8f Patel M, Saunthwal RK, Verma AK. Acc. Chem. Res. 2017; 50: 240

9a Doucet H, Bruneau C, Dixneuf PH. Synlett 1997; 807
9b Leitch DC, Payne PR, Dunbar CR, Schafer LL. J. Am. Chem. Soc. 2009; 131: 18246
9c Kocięcka P, Czcluśniak I, Szymańska-Buzar T. Adv. Synth. Catal. 2014; 356: 3319
9d Slagbrand T, Vockov A, Trillo P, Tinnis F, Adolfsson H. ACS Catal. 2017; 7: 1771

For Pd-catalyzed hydroamination, see:

10a Shimada T, Yamamoto Y. J. Am. Chem. Soc. 2002; 124: 12670
10b Salman GA, Hussain M, Iaroshenko V, Villinger A, Langer P. Adv. Synth. Catal. 2011; 353: 331
10c Bernhammer JC, Chong NX, Jothibasu R, Zhou B, Huynh HV. Organometallics 2014; 33: 3607
10d Banerjee D, Junge K, Beller M. Angew. Chem. Int. Ed. 2014; 53: 1630 ; Corrigendum: Angew. Chem. Int. Ed. 2017, 56, 16436
10e Lhristodoulou MS, Giofrè S, Broggini G, Mazza A, Sala R, Beccalli EM. Eur. J. Org. Chem. 2018; 6176
10f Park S, Malcolmson SJ. ACS Catal. 2018; 8: 8468

For Rh-catalyzed hydroamination, see:

11a Fukumoto Y, Asai H, Shimizu M, Chatani N. J. Am. Chem. Soc. 2007; 129: 13792
11b Utsusomiya M, Kuwano R, Kawatsura M, Hartwig JF. J. Am. Chem. Soc. 2003; 125: 5608
11c Shen X, Buchwald SL. Angew. Chem. Int. Ed. 2010; 49: 564
11d Sakai K, Kochi T, Kakiuchi F. Org. Lett. 2011; 13: 3928
11e Takano S, Kochi T, Kakiuchi F. Organometallics 2016; 35: 4112
11f Yang X.-H, Lu A, Dong VM. J. Am. Chem. Soc. 2017; 139: 14049
11g Athira C, Changotra A, Sunoj RB. J. Org. Chem. 2018; 83: 2627
11h Yang S, Li Q, Xu C, Xu Q, Shi M. Chem. Sci. 2018; 9: 5074

For Au-catalyzed hydroamination, see:

12a Kang J.-E, Kim H.-B, Lee J.-W, Shin S. Org. Lett. 2006; 8: 3537
12b Lavallo V, Frey GD, Donnadieu B, Soleilhavoup M, Bertrand G. Angew. Chem. Int. Ed. 2008; 47: 5224
12c Zeng X, Frey GD, Kinjo R, Donnadieu B, Bertrand G. J. Am. Chem. Soc. 2009; 131: 8690
12d Couce-Rios A, Kovács G, Ujaque G, Lledós A. ACS Catal. 2015; 5: 815
12e Timmerman JC, Robertson BD, Widenhoefer RA. Angew. Chem. Int. Ed. 2015; 54: 2251
12f Wang Y, Ling B, Li P, Bi S. Organometallics 2018; 37: 3035
12g Liu D, Nie Q, Zhang R, Cai M. Adv. Synth. Catal. 2018; 360: 3940
12h Baron M, Battistel E, Tubaro C, Biffis A, Armelao L, Ramcan M, Graiff C. Organometallics 2018; 37: 4213

13a Stephens RD, Castro CE. J. Org. Chem. 1963; 28: 2163
13b Stephens RD, Castro CE. J. Org. Chem. 1963; 28: 3313
13c Kimura M, Kure S, Yoshida Z, Tanaka S, Fugami K, Tamaru Y. Tetrahedron Lett. 1990; 31: 4887

14a Zhou L, Bohle DS, Jiang H.-F, Li C.-J. Synlett 2009; 937
14b Robbins DW, Hartwig JF. Science 2011; 333: 1423
14c Shi S.-L, Buchwald SL. Nat. Chem. 2015; 7: 38

15 Bahri J, Jamoussi B, Lee AV. D, Taillefer M, Monnier F. Org. Lett. 2015; 17: 1224
16 Bahri J, Blieck R, Jamoussi B, Taillefer M, Monnier M. Chem. Commun. 2015; 51: 11210

Beauchemin’s group has recently developed a series of Cope-type hydroaminations of alkenes and alkynes; see:

17a Beauchemin AM, Moran J, Lebrun M.-E, Séguin C, Dimitrijevic E, Zhang L, Gorelsky SI. Angew. Chem. Int. Ed. 2008; 47: 1410
17b Cebrowski PH, Roveda JG, Moran J, Gorelsky SI, Beauchemin AM. Chem. Commun. 2008; 492
17c Moran J, Gorelsky SI, Dimitrijevic E, Lebrun ME, Bédard A.-C, Séguin C, Beauchemin AM. J. Am. Chem. Soc. 2008; 130: 17893
17d Moran J, Pfeiffer JY, Gorelsky SI, Beauchemin AM. Org. Lett. 2009; 11: 1895
17e Loiseau F, Clavette C, Raymond M, Roveda JG, Beauchemin AM. Chem. Commun. 2011; 47: 562
17f Bourgeois J, Dion I, Cebrowski PH, Loiseau F, Bédard A.-C, Beauchemin AM. J. Am. Chem. Soc. 2009; 131: 874
17g Zhao S.-B, Bilodeau E, Lemieux V, Beauchemin AM. Org. Lett. 2012; 14: 5082
17h Beauchemin AM. Org. Biomol. Chem. 2013; 11: 7039

18 For a metal-free intermolecular hydroamidation of ynamides with N-sulfonamides, see: Peng Z, Zhang Z, Tu Y, Zeng X, Zhao J. Org. Lett. 2018; 20: 5688
19 Clarke CJ, Tu W.-C, Levers O, Bröhl A, Hallett JP. Chem. Rev. 2018; 118: 747
20 It is also possible to recover the unused amine in a cold trap and then totally recycle it.
21 Propargyl alcohol and oct-1-yne have also been tested; however, no product was obtained. This probably demonstrates that the solvent is the sole source of hydrogen bonding.
22 Hydroamination of Alkynes with Amines; General Procedure Under an atmosphere of argon, a screw-cap vial was charged with ethylene glycol (250 μL, 8.9 equiv) and the appropriate alkyne (0.5 mmol, 1 equiv) and amine (2.5 mmol) at r.t. The tube was sealed under a positive pressure of argon and the mixture was stirred and heated to 150 °C for 8 h. The mixture was cooled to r.t., diluted with EtOAc (5 mL), and washed with H₂O (3 × 2 mL) and brine (1 × 2 mL). The organic phase was dried (MgSO₄), filtered, and concentrated under reduced pressure (rotary evaporator). Excess amine was then removed from the residue under high vacuum to give the desired enamine without any need for further purification. In the case of amines with high boiling points, such as dibutylamine or dipentylamine, the residues were dried by heating to 50 °C under high vacuum. (E)-N,N-Dipentyl-2-phenylethylenamine (3b) Solid; yield: 97 mg (75%). ¹H NMR (400 MHz, CDCl₃): δ = 7.20–7.14 (m, 4 H), 6.95–6.92 (m, 1 H), 6.76 (d, J = 14 Hz, 1 H), 5.07 (d, J = 14 Hz, 1 H), 3.07 (t, J = 7.1 Hz, 4 H), 1.60–1.54 (m, 4 H), 1.39–1.33 (m, 4 H), 1.33–1.28 (m, 4 H), 0.92 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 140.4, 138.5, 128.5, 123, 122.5, 96.3, 51.7, 29.2, 27.6, 22.5, 14.1. HRMS (ESI-TOF): m/z [M + H]⁺ Calcd for C₁₈H₃₀N: 260.2300; found: 260.2301.

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