Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2013; 24(2): 193-196
DOI: 10.1055/s-0032-1317843
DOI: 10.1055/s-0032-1317843
letter
Substrate Structural Effects in Yttrium(III)-Catalyzed Hydroamination/Cyclizations of 1,2-Disubstituted and 1,1,2-Trisubstituted Aminoalkenes Terminated by 2-(Phenyl) and 2-(2-Heteroarenyl) Groups
Further Information
Publication History
Received: 03 October 2012
Accepted after revision: 06 November 2012
Publication Date:
12 December 2012 (online)
Abstract
A series of 2-phenyl- and 2-(2-heteroarenyl)-bearing amines possessing 1,2-disubstituted and 1,1,2-trisubststuted alkenes have been evaluated in intramolecular hydroaminations catalyzed by Y[N(TMS)2]3 (1Y ). Aminoalkenes possessing a terminal 2-(5-trimethylsilyl)thienyl group exhibited substantially enhanced reactivity compared to their 2-(phenyl)-containing counterparts. Cyclization efficiencies imparted by the 2-[(5-trimethylsilyl)furanyl] substituent were comparable or only slightly better than those obtained with the simple the 2-(phenyl) group.
Supporting Information
- for this article is available online at http://www.theme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1a Crimmin MR, Arrowsmith M, Barrett AG. M, Casely IJ, Hill MS, Procoplou PA. J. Am. Chem. Soc. 2009; 131: 9670 ; and references cited therein
- 1b Ogata T, Atsushi U, Susumu T, Tomoko S, Atsunori K, Kiyoshi T. Tetrahedron Lett. 2007; 48: 6648
- 1c Matsunaga S. Yuki Gosei Kagaku Kyokaishi 2006; 64: 778
- 1d Takemiya A, Hartwig JF. J. Am. Chem. Soc. 2006; 128: 6042
- 1e Bauer EB, Andavan GT. S, Hollis TK, Rubio RJ, Cho J, Kuchenbeiser GR, Helgert TR, Letko CS, Tham FS. Org. Lett. 2008; 10: 1175
- 1f Takaya J, Hartwig JF. J. Am. Chem. Soc. 2005; 127: 5756
- 1g Knodo T, Okada T, Suzuki T, Mitsudo T. J. Organomet. Chem. 2001; 622: 149
- 1h Fadini L, Togni A. Tetrahedron: Asymmetry 2008; 19: 2555
- 1i Fadani L, Togni A. Chem. Commun. 2003; 1: 30
- 1j Pawlas J, Nakao Y, Kawatsura M, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 3669
- 1k Cochran BM, Michael FE. J. Am. Chem. Soc. 2008; 130: 2786
- 1l Michael FE, Cochran BM. J. Am. Chem. Soc. 2006; 128: 4246
- 1m Nettekoven U, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 1166
- 1n Narsireddy M, Yamamoto Y. J. Org. Chem. 2008; 73: 9698
- 1o Shaffer AR, Schmidt JA. R. Organometallics 2008; 27: 1259
- 1p Siriwardana AI, Kamada M, Nakamura I, Yamamoto Y. J. Org. Chem. 2005; 70: 5932
- 1q Shimada T, Yamamoto Y. J. Am. Chem. Soc. 2002; 124: 12670
- 1r LaLond RL, Wang ZJ, Mba M, Lackner AD, Toste FD. Angew. Chem. Int. Ed. 2010; 49: 598
- 1s Widenhofer RA, Han X. Eur. J. Org. Chem. 2006; 4555 ; and references cited therein
- 1t Leseurre L, Toullec PV, Genet J, Michelet V. Org. Lett. 2007; 9: 4049
- 2a Hong S, Marks TJ. Acc. Chem. Res. 2004; 37: 673 ; and references cited therein
- 2b Jiang T, Livinghouse T. Org. Lett. 2010; 12: 4271
- 2c Kim JY, Livinghouse T. Org. Lett. 2005; 7: 4391
- 2d Kim YK, Livinghouse T. Angew. Chem. Int. Ed. 2002; 41: 3645
- 2e Tian S, Arredondo VM, Stern CL, Marks TJ. Organometallics 1999; 18: 2568
- 2f Gribkov DV, Hultzsch KC, Hampel F. J. Am. Chem. Soc. 2006; 128: 3748 ; and references cited therein
- 2g Kim YK, Livinghouse T, Horino Y. J. Am. Chem. Soc. 2003; 125: 9560
- 2h Kim JY, Livinghouse T. Org. Lett. 2005; 7: 1737
- 2i Kim YK, Livinghouse T, Bercaw JE. Tetrahedron Lett. 2001; 42: 2933
- 2j Lauterwasser F, Hayes PG, Brase S, Piers WE, Schafer LL. Organometallics 2004; 23: 2234
- 2k Hannedouche J, Aillaud I, Collin J, Schulz E, Trifonov A. Chem. Commun. 2008; 3552
- 2l Aillaud I, Collin J, Duhayon C, Guillot R, Lyubov D, Schulz E, Trifonov A. Chem.–Eur. J. 2008; 14: 2189
- 2m Yu X, Marks T. Organometallics 2007; 26: 365
- 2n Marks TJ, Hong S. J. Am. Chem. Soc. 2002; 124: 7886
- 2o Chapurina Y, Hannedouche J, Collin J, Guillot G, Schulz E, Trifonov A. Chem. Commun. 2010; 46: 6918
- 2p Leitch DC, Payne PR, Dunbar CR, Schafer LL. J. Am. Chem. Soc. 2009; 131: 18246
- 2q Reznichenko AL, Hultzsch KC. Organometallics 2010; 29: 24
- 2r Wood MC, Leitch DC, Yeung CS, Kozak JA, Schafer LL. Angew. Chem. Int. Ed. 2007; 46: 354
- 2s Kim H, Lee PH, Livinghouse T. Chem. Commun. 2005; 41: 5205
- 2t Kim H, Kim YK, Shim JH, Kim M, Han M, Livinghouse T, Lee PH. Adv. Synth. Catal. 2006; 348: 2609
- 2u Thomson RK, Bexrud JA, Schafer LL. Organometallics 2006; 25: 4069
- 2v Kubiak R, Prochnow I, Doye S. Angew. Chem. Int. Ed. 2009; 48: 1153
- 2w Watson DA, Chiu M, Bergman RG. Organometallics 2006; 25: 4731
- 2x Mueller C, Loos C, Schulenberg N, Doye S. Eur. J. Org. Chem. 2006; 2499
- 2y Bexrud JA, Beard JD, Leitch DC, Schafer LL. Org. Lett. 2005; 7: 1959
- 2z Mueller C, Koch R, Doye S. Chem.–Eur. J. 2008; 14: 10430
- 3 All 1H NMR yields are based on integration relative to p-xylene as the internal standard.
- 4 Tobisch S. Dalton Trans. 2012; 9182
- 5 For a recent study involving the hydroamination/cyclization of a small set of 1,1,2-trisubstituted aminoalkenes, see: Chapurina Y, Ibrahim H, Guillot R, Kolodziej E, Collin J, Trifonov A, Schulz E, Hannedouche J. J. Org. Chem. 2011; 76: 10163
- 6a Baig MA, Banthorp DV, Carr G, Whittaker D. J. Chem. Soc., Perkin Trans. 2 1989; 1981
- 6b Iovel’ IG, Goldberg YS, Shimanskaya M In The Chemistry of Heterocyclic Compounds . Vol. 27, No. 12. Springer; New York: 1991: 1316-1318
- 7a General Cyclization/Hydroamination Procedure: In an argon-filled glove box, Y[N(TMS)2]3 (5.70 mg, 0.010 mmol) and benzene-d 6 (0.5 mL) were added into a J. Young NMR tube equipped with a Teflon screw cap. (E)-2,2,4-Trimethyl-5-[5-(trimethylsilyl)-2-thienyl]pent-4-enylamine (3f; 28 mg, 0.10 mmol) and p-xylene (10 µL) were then added and the reactant mixture was subsequently held at 60 °C in an oil bath for 4 h until cyclization/hydroamination was judged complete (≥95% by 1H NMR integration).
- 7b Synthesis of p-Toluenesulfonamide; 2,4,4-Trimethyl-1-(toluene-4-sulfonyl)-2-[5-(trimethylsilyl)thiophene-2-ylmethyl]tetrahydropyrrole (4fTs): Tetrahydropyrrole 4f was prepared from (E)-2,2,4-trimethyl-5-[5-(trimethylsilyl)-2-thienyl]pent-4-enylamine (3f; 28 mg, 0.10 mmol) by the general hydroamination procedure. The Teflon screw cap was then removed and the crude product was diluted with anhydrous CH2Cl2 (3 mL). TsCl (22 mg, 0.12 mmol) and pyridine (9.70 μL, 0.12 mmol) were added in succession. The reactant mixture was stirred at room temperature for 12 h, then the reactant mixture was diluted with Et2O (10 mL), washed with saturated NaHCO3 (3 mL) and brine (3 mL), and the organic phase was subsequently dried with Na2SO4. Concentration in vacuo followed by flash chromatography on silica gel (hexane–EtOAc, 15:1) afforded 2,4,4-trimethyl-1-(toluene-4-sulfonyl)-2-[5-(trimethylsilyl)thiophene-2-ylmethyl]tetrahydropyrrole (4fTs ; 33.2 mg, 76%). 1H NMR (500 MHz, CDCl3): δ = 7.75 (d, J = 8.0 Hz, 2 H, 2Ar-H), 7.26 (d, J = 8.0 Hz, 2 H, 2Ar-H), 7.07 (d, J = 3.0 Hz, 1 H, Ar-H), 6.98 (d, J = 3.0 Hz, 1 H, Ar-H), 3.57 (d, J = 14.0 Hz, 1 H, CH), 3.29 (d, J = 14.0 Hz, 1 H, CH), 3.06 (d, J =9.5 Hz, 1 H, CH), 2.98 (d, J = 10.0 Hz, 1 H, CH), 2.40 (s, 3 H, ArCH3), 2.15 (d, J = 13.0 Hz, 1 H, CH), 1.51 (s, 3 H, CH3), 1.42 (d, J = 13.5 Hz, 1 H, CH), 0.97 (s, 3 H, CH3), 0.90 (s, 3 H, CH3), 0.27 (s, 9 H, 3 SiCH3); 13C NMR (500 MHz, CDCl3): δ = 145.2, 142.8, 138.4, 133.9, 129.4, 129.3, 127.3, 68.7, 61.8, 52.6, 42.3, 36.2, 27.6, 27.2, 27.1, 21.5, −0.02; IR (film): 2957, 1439, 1342, 1251, 1209, 1154, 1092, 1055, 984, 840, 814, 759, 714, 659, 592, 548 cm−1; HRMS (ESI): m/z [M + H]+ calcd for C22H33NO2S2Si: 436.1816; found: 436.1897.