Aza-Reformatsky Reaction Promoted by Catalytic Samarium Diiodide: Synthesis of β-Amino Esters or Amides

Humberto Rodríguez-Solla; Ainhoa Díaz-Pardo; Carmen Concellón; Vicente del Amo

doi:10.1055/s-0034-1378229

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(12): 1709-1712
DOI: 10.1055/s-0034-1378229

letter

Aza-Reformatsky Reaction Promoted by Catalytic Samarium Diiodide: Synthesis of β-Amino Esters or Amides

Humberto Rodríguez-Solla*

Dpto. Química Orgánica e Inorgánica, Universidad de Oviedo, C/ Julián Clavería 8, 33006 Oviedo, Spain eMail: hrsolla@uniovi.es

,

Ainhoa Díaz-Pardo

Dpto. Química Orgánica e Inorgánica, Universidad de Oviedo, C/ Julián Clavería 8, 33006 Oviedo, Spain eMail: hrsolla@uniovi.es

,

Carmen Concellón

Dpto. Química Orgánica e Inorgánica, Universidad de Oviedo, C/ Julián Clavería 8, 33006 Oviedo, Spain eMail: hrsolla@uniovi.es

,

Vicente del Amo

Dpto. Química Orgánica e Inorgánica, Universidad de Oviedo, C/ Julián Clavería 8, 33006 Oviedo, Spain eMail: hrsolla@uniovi.es

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Abstract

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Abstract

The synthesis of β-amino esters or amides has been achieved from moderate to high yields from the reaction of imines and α-halo esters or amides promoted by catalytic amounts of samarium diiodide in the presence of magnesium turnings as co-reductant. A mechanism is proposed to explain this catalytic samarium(II)-promoted aza-Reformatsky reaction.

Key words

amino esters - catalytic reactions - enolates - Reformatsky reaction - samarium

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Referenzen

References and Notes

For reviews on the synthesis of β-amino acids, see:

1a Cole DC. Tetrahedron 1994; 50: 9517
1b Enantioselective Synthesis of β-Amino Acids. Juaristi E. Wiley-VCH; New York: 1997
1c Juaristi E, López-Ruiz H. Curr. Med. Chem. 1999; 6: 983
1d Abele S, Seebach D. Eur. J. Org. Chem. 2000; 1
1e Lui M, Sibi M. Tetrahedron 2002; 58: 7991
1f Davies SG, Smith AD, Price PD. Tetrahedron: Asymmetry 2005; 16: 2833
1g Sleebs BE, Van Nguyen TT, Hughes AB. Org. Prep. Proced. Int. 2009; 41: 429

For recent papers on the synthesis of β-amino acids, see:

1h Shen B, Johnston JN. Org. Lett. 2008; 10: 4397
1i Yang JW, Chandler C, Stadler M, Kampen D, List B. Nature (London, U.K.) 2008; 452: 453
1j Seayad J, Patra PK, Zhang Y, Ying JY. Org. Lett. 2008; 10: 953
1k Lu X, Deng L. Angew. Chem. Int. Ed. 2008; 47: 7710
1l Martin NJ. A, Cheng X, List B. J. Am. Chem. Soc. 2008; 130: 13862
1m Malkov AV, Stončius S, Vranková K, Arndt M, Kočovský P. Chem. Eur. J. 2008; 14: 8082
1n Nolte GT, Baxter VuJ. M, Leighton JL. Org. Lett. 2011; 13: 816
1o Bea S.-H, Park H.-J, Lee S.-H, Yun H. Chem. Commun. 2011; 47: 5894
1p Wang Q, Leutzsch M, van Gemmeren M, List B. J. Am. Chem. Soc. 2013; 135: 15334

2 Sewald N. Angew. Chem. Int. Ed. 2003; 42: 5794

β-Amino acids can be transformed into other compounds. Piperidines:

3a Jefford CW, Wang JB. Tetrahedron Lett. 1993; 34: 2911
3b Davis FA, Santhanaraman M. J. Org. Chem. 2006; 71: 4222
3c Davies SG, Hughes DG, Price PD, Roberts PM, Russell AJ, Smith AD, Thomson JE, Williams OM. H. Synlett 2010; 567

Indolizidines:

3d Jefford CW, Wang JB. Tetrahedron Lett. 1993; 34: 3119
3e Davis FA, Yang B. Org. Lett. 2003; 5: 5011
3f Davis FA, Yang B. J. Am. Chem. Soc. 2005; 127: 8398

β-Lactams:

3g Juaristi E, Quintana D, Escalante J. Aldrichimica Acta 1994; 27: 3
3h Tzouvelekis LS, Bonomo RA. Curr. Pharm. Des. 1999; 5: 847
3i Massova I, Mobashery S. Curr. Pharm. Des. 1999; 5: 929
3j Mascaretti OA, Danelon GO, Laborde M, Mata EG, Setti EL. Curr. Pharm. Des. 1999; 5: 939
3k Garau G, García-Sáez I, Bebrone C, Anne C, Mercuri P, Galleen M, Frere JM, Dideberg O. Antimicrob. Agents Chemother. 2004; 48: 2347
3l Ozeki M, Ochi S, Hayama N, Hosoi S, Kajimoto T, Node M. J. Org. Chem. 2010; 75: 4201

4a Drey CN. C In Chemistry and Biochemistry of the Amino Acids . Barret GC. Chapman and May; New York: 1985. Chap. 3
4b Griffith OW. Annu. Rev. Biochem. 1986; 55: 855

5a Tramontini M, Angiolini L In Mannich-Bases: Chemistry and Uses . CRC; Boca Raton, FL: 1994
5b Cardillo G, Tomasini C. Chem. Soc. Rev. 1996; 117
5c Enantioselective Synthesis of β-Amino Acids . Juaristi E, Soloshonok VA. Wiley-VCH; New York: 2005

For reviews on β-peptides, see:

6a Gellman SH. Acc. Chem. Res. 1998; 31: 173
6b Seebach D, Abele S, Gademann K, Jaun B. Angew. Chem. Int. Ed. 1999; 38: 1595

7 Krauthäuser S, Christianson LA, Powell DR, Gellman SH. J. Am. Chem. Soc. 1997; 119: 11719

8a Concellón JM, Rodríguez-Solla H, Simal C. Adv. Synth. Catal. 2009; 351: 1238
8b Concellón JM, Rodríguez-Solla H, Simal C, del Amo V, García-Granda S, Díaz MR. Adv. Synth. Catal. 2009; 351: 2991

For recent reviews of SmI₂, see:

9a Edmons DJ, Johnston D, Procter DJ. Chem. Rev. 2004; 104: 3371
9b Concellón JM, Rodríguez-Solla H. Chem. Soc. Rev. 2004; 33: 599
9c Jung D, Kim YH. Synlett 2005; 3019
9d Concellón JM, Rodríguez-Solla H. Eur. J. Org. Chem. 2006; 1613
9e Kagan HB, Gopalaiah K. New J. Chem. 2008; 32: 607
9f Rudkin IM, Miller LC, Procter DJ. Organomet. Chem. 2008; 34: 19
9g Nicolau KC, Ellery SP, Chen JS. Angew. Chem. Int. Ed. 2009; 48: 7140
9h Concellón JM, Rodríguez-Solla H, Concellón C, del Amo V. Chem. Soc. Rev. 2010; 39: 4103
9i Procter DJ, Flowers RA. II, Skrydstrup T. Organic Synthesis Using Samarium Diiodide: A Practical Guide . Royal Society of Chemistry Publishing; Cambridge: 2010
9j Szostak M, Spain M, Parmar D, Procter DJ. Chem. Commun. 2012; 330
9k Harb HY, Procter DJ. Synlett 2012; 23: 6
9l Szostak M, Spain M, Procter DJ. Chem. Soc. Rev. 2013; 42: 9155

10 Corey EJ, Zheng GZ. Tetrahedron 1997; 12: 2045

11a Hélion F, Namy J.-L. J. Org. Chem. 1997; 64: 2944
11b Lannon M.-I, Hélion F, Namy J.-L. Tetrahedron 2003; 59: 10551

12 Orsini F, Lucci EM. Tetrahedron Lett. 2005; 46: 1909
13 Nomura R, Matsuno T, Endo T. J. Am. Chem. Soc. 1996; 118: 11666
14 Aspinall HC, Greeves N, Valla C. Org. Lett. 2005; 10: 1919
15 Hébri H, Dunach E, Heintz M, Troupel M, Périchon J. Synlett 1991; 901
16 Sun L, Sahloul K, Mellah M. ACS Catal. 2013; 3: 2568
17 Concellón JM, Rodríguez-Solla H, Concellón C, Díaz-Pardo A, Llavona R. Synlett 2011; 262
18 Wang Y, Song J, Hong R, Li H, Deng L. J. Am. Chem. Soc. 2006; 128: 8156
19 Procedure for the Synthesis of N-Tosyloctan-1-imine (1a) A mixture of n-octanal (10 mmol), p-toluenesulfonamide (10 mmol), sodium p-toluenesulfinate (10 mmol) in H₂O (15 mL), and formic acid (15 mL) was stirred for 24 h at r.t. The resulting white precipitate was collected by filtration, washed with H₂O (3 × 10 mL) and hexane (2 × 10 mL), then dissolved in CH₂Cl₂ (100 mL), followed by addition of H₂O (35 mL) and sat. aq NaHCO₃ (35 mL). The solution was well stirred for 10 min at r.t. The organic phase was collected, the aqueous phase was extracted with CH₂Cl₂ (3 × 70 mL). The combined organic layers were dried over Na₂SO₄ and concentrated in vacuo to yield N-tosyloctan-1-imine (1a) as a colorless oil (1.84 g, 65%). This material was used without further purification. ¹H NMR (300 MHz, CDCl₃): δ = 8.60 (t, J = 4.6 Hz, 1 H), 7.81 (d, J = 8.2 Hz, 2 H), 7.34 (d, J = 8.2 Hz, 2 H), 2.51 (dt, J = 7.4, 4.6 Hz, 2 H), 2.40 (s, 3 H), 1.66–1.57 (m, 2 H), 1.39–1.14 (m, 8 H), 0.86 (t, J = 6.8 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 178.4 (CH), 144.4 (C), 134.4 (C), 129.5 (2 × CH), 127.8 (2 × CH), 35.6 (CH₂), 31.2 (CH₂), 28.7 (CH₂), 28.5 (CH₂), 24.3 (CH₂), 22.2 (CH₂), 21.3 (CH₃), 13.7 (CH₃). IR (neat): ν = 3292, 1629, 1020, 737 cm^–1.
20 Please note that a minimum of 2.0 equiv of SmI₂ are required to carry out this transformation in a stoichiometric manner.
21 Since magnesium is normally coated with a layer of MgO, we have previously treated the magnesium turnings with a few crystals of iodine to activate its surface.
22 Procedure for the Synthesis of Ethyl 3-(Tosylamino)-decanoate (3a) A solution of N-tosyloctan-1-imine (1a, 0.2 mmol) and ethyl bromoacetate (2a, 0.2 mmol) in THF (2.5 mL) was added dropwise at r.t. and vigorous stirring to a mixture of SmI₂ (0.1 M in THF, 0.8 mL) and activated Mg (1.2 mmol) with iodine and ZnCl₂ (1.2 mmol) in THF (2.5 mL). After stirring at the same temperature 3.5 h, the mixture was hydrolyzed with an aq solution of HCl (0.1 M, 10 mL). The aqueous phase was filtered through a pad of Celite^® and extracted with CH₂Cl₂ (3 × 10 mL). The combined organic extracts were dried over Na₂SO₄ and concentrated in vacuo. Flash column chromatography on silica gel (hexane–EtOAc, 5:1) provided pure ethyl 3-(tosylamino)decanoate (3a) as a yellow oil (62 mg, 83%). ¹H NMR (300 MHz, CDCl₃): δ = 7.69 (d, J = 8.0 Hz, 2 H), 7.21 (d, J = 8.0 Hz, 2 H), 5.22 (d, J = 9.0 Hz, 1 H), 4.09–3.92 (m, 2 H), 3.50–3.38 (m, 1 H), 2.51 (ddd, J = 3.0, 15.0, 30.0 Hz, 2 H), 2.35 (s, 3 H), 1.47–1.06 (m, 12 H), 1.15 (t, J = 7.0 Hz, 3 H), 0.79 (t, J = 7.0 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 171.3 (C), 143.1 (C), 138.1 (C), 129.5 (2 × CH), 126.8 (2 × CH), 60.5 (CH₂), 50.6 (CH), 41.2 (CH₂), 38.8 (CH₂), 34.6 (CH₂), 31.6 (CH₂), 29.1 (CH₂), 28.9 (CH₂), 25.6 (CH₂), 22.5 (CH₃), 21.4 (CH₃), 13.9 (CH₃). IR (neat): ν = 1747, 1331, 1160, 1094 cm^–1. HRMS: m/z calcd for C₁₉H₃₂NO₄S [M + H]⁺: 370.2052; found: 370.2049.
23 For the synthesis of N-Boc imine 1g, see: Wenzel AG, Jacobsen EN. J. Am. Chem. Soc. 2002; 124: 12964
24 Molander GA, Stengel PJ. J. Org. Chem. 1995; 60: 6660
25 Spectroscopic Data of Compound 3e ¹H NMR (300 MHz, CDCl₃): δ = 7.54 (d, J = 8.2 Hz, 2 H), 7.14–7.10 (m, 5 H), 6.93 (d, J = 8.2 Hz, 2 H), 5.21 (d, J = 8.2 Hz, 1 H), 4.08–3.92 (m, 2 H), 3.74–3.63 (m, 1 H), 2.72 ( d, J = 6.0 Hz, 1 H), 2.71 (d, J = 6.0 Hz, 1 H), 2.37 (d, J = 5.2 Hz, 2 H), 2.32 (s, 3 H), 1.15 (t, J = 7.1 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 171.6 (C), 143.5 (C), 137.8 (C), 137.1 (C), 129.9 (2 × CH), 129.6 (2 × CH), 128.9 (2 × CH), 127.3 (2 × CH), 127.0 (CH), 61.0 (CH₂), 52.2 (CH), 41.0 (CH₂), 38.3 (CH₂), 21.8 (CH₃), 14.4 (CH₃). IR (neat): ν = 2929, 1740, 1265, 1160, 738 cm^–1. HRMS: m/z calcd for C₁₉H₂₄NO₄S [M + H]⁺: 362.1426; found: 362.1428.