Synlett 2016; 27(04): 559-563
DOI: 10.1055/s-0035-1650585
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© Georg Thieme Verlag Stuttgart · New York

Highly Enantioselective Intermolecular Iodo- and Chloroamination of Enecarbamates Catalyzed by Chiral Phosphoric Acids or Calcium Phosphate Salts

Clément Lebée
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Univ. Paris-Sud, Univ. Paris-Saclay, 1, av. de la Terrasse, 91198 Gif-sur-Yvette Cedex, France   Email: geraldine.masson@cnrs.fr
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Florent Blanchard
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Univ. Paris-Sud, Univ. Paris-Saclay, 1, av. de la Terrasse, 91198 Gif-sur-Yvette Cedex, France   Email: geraldine.masson@cnrs.fr
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Géraldine Masson*
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Univ. Paris-Sud, Univ. Paris-Saclay, 1, av. de la Terrasse, 91198 Gif-sur-Yvette Cedex, France   Email: geraldine.masson@cnrs.fr
› Author Affiliations
Further Information

Publication History

Received: 21 August 2015

Accepted after revision: 09 October 2015

Publication Date:
09 November 2015 (online)


Abstract

Highly enantio- and diastereoselective vicinal chloro- and iodoamination reaction of enecarbamates catalyzed by chiral phosphoric acids or chiral calcium organophosphates are reported. The approach described herein provides efficient access to cis-chloro and cis-iodoaminals in good yields and excellent enantioselectivities (up to 99% ee). The resulting products are converted readily into highly important trans-azidoaminals.

Supporting Information

 
  • References and Notes


    • For reviews on aminohalogenation of olefins, see:
    • 1a Chemler SR, Bovino MT. ACS Catal. 2013; 3: 1076
    • 1b Li G, Kotti SR. S. S, Timmons C. Eur. J. Org. Chem. 2007; 2745

    • See also:
    • 1c Denmark SE, Kuester WE, Burk MT. Angew. Chem. Int. Ed. 2012; 51: 10938

      For some representatives examples, see:
    • 2a Hamilton GL, Kanai T, Toste FD. J. Am. Chem. Soc. 2008; 130: 14984
    • 2b Yeung Y.-Y, Gao X, Corey EJ. J. Am. Chem. Soc. 2006; 128: 9644
    • 2c Qiu J, Silverman RB. J. Med. Chem. 2000; 43: 706
    • 2d Griffith DA, Danishefsky SJ. J. Am. Chem. Soc. 1991; 113: 5863
    • 2e Griffith DA, Danishefsky SJ. J. Am. Chem. Soc. 1990; 112: 5811
    • 2f Barton DH. R, Britten-Kelley MR, Ferreira D. J. Chem. Soc., Perkin Trans. 1 1978; 1090

      For leading references on intramolecular enantioselective aminohalogenation of olefins, see:
    • 3a Liu W, Pan H, Tian H, Shi Y. Org. Lett. 2015; 17: 3956
    • 3b Sakakura A, Ishihara K. Chem. Rec. 2015; 15: 728
    • 3c Cai Y, Zhou P, Liu X, Zhao J, Lin L, Feng X. Chem. Eur. J. 2015; 21: 6386
    • 3d Tripathi CB, Mukherjee S. Org. Lett. 2014; 16: 3368
    • 3e Mizar P, Burrelli A, Günther E, Söftje M, Farooq U, Wirth T. Chem. Eur. J. 2014; 20: 13113
    • 3f Brindle CS, Yeung CS, Jacobsen EN. Chem. Sci. 2013; 4: 2100
    • 3g Chen F, Tan CK, Yeung Y.-Y. J. Am. Chem. Soc. 2013; 135: 1232
    • 3h Zhou L, Tay DW, Chen J, Leung GY. C, Yeung Y.-Y. Chem. Commun. 2013; 49: 4412
    • 3i Miles DH, Veguillas M, Toste FD. Chem. Sci. 2013; 4: 3427
    • 3j Brindle CS, Yeung CS, Jacobsen EN. Chem. Sci. 2013; 4: 2100
    • 3k Chen F, Tan CK, Yeung Y.-Y. J. Am. Chem. Soc. 2013; 135: 1232
    • 3l Bovino MT, Chemler SR. Angew. Chem. Int. Ed. 2012; 51: 3923
    • 3m Chen J, Zhou L, Yeung Y.-Y. Org. Biomol. Chem. 2012; 10: 3808
    • 3n Lozano O, Blessley G, Campo TM, Thompson AL, Giuffredi GT, Bettati M, Walker M, Borman R, Gouverneur V. Angew. Chem. Int. Ed. 2011; 50: 8105
    • 3o Liu N, Werness JB, Guzei IA, Tang W. Tetrahedron 2011; 67: 4385
    • 3p Zhou L, Chen J, Tan CK, Yeung Y.-Y. J. Am. Chem. Soc. 2011; 133: 9164
    • 3q Huang D, Wang H, Xue F, Guan H, Li L, Peng X, Shi Y. Org. Lett. 2011; 13: 6350

      For leading references, see:
    • 4a Denmark SE, Burk MT, Hoover AJ. J. Am. Chem. Soc. 2010; 132: 1232
    • 4b Brown RS. Acc. Chem. Res. 1997; 30: 131
    • 5a Cai Y, Liu X, Jiang J, Chen W, Lin L, Feng X. J. Am. Chem. Soc. 2011; 133: 5636
    • 5b Cai Y, Liu X, Li J, Chen W, Wang W, Lin L, Feng X. Chem. Eur. J. 2011; 17: 14916
    • 5c Cai Y, Liu X, Hui Y, Jiang J, Wang W, Chen W, Lin L, Feng X. Angew. Chem. Int. Ed. 2010; 49: 6160
  • 6 Alix A, Lalli C, Retailleau P, Masson G. J. Am. Chem. Soc. 2012; 134: 10389
    • 7a Kano T, Yurino T, Asakawa D, Maruoka K. Angew. Chem. Int. Ed. 2013; 52: 5532
    • 7b Kano T, Yurino T, Maruoka K. Angew. Chem. Int. Ed. 2013; 52: 11509
    • 7c Vellalath S, Čorić I, List B. Angew. Chem. Int. Ed. 2010; 49: 9749
    • 7d Cheng X, Vellalath S, Goddard R, List B. J. Am. Chem. Soc. 2008; 130: 15786
    • 7e Liang Y, Rowland EB, Rowland GB, Perman JA, Antilla JC. Chem. Commun. 2007; 4477

      For recent reviews on chiral phosphoric acid catalysis, see:
    • 8a Parmar D, Sugiono E, Raja S, Rueping M. Chem. Rev. 2014; 114: 9047
    • 8b Mahlau M, List B. Angew. Chem. Int. Ed. 2013; 52: 518
    • 8c Rueping M, Kuenkel A, Atodiresei I. Chem. Soc. Rev. 2011; 40: 4539
    • 8d Kampen D, Reisinger CM, List B. Top. Curr. Chem. 2010; 291: 395
    • 8e Terada M. Bull. Chem. Soc. Jpn. 2010; 83: 101
    • 8f Terada M. Synthesis 2010; 1929
    • 8g Terada M. Chem. Commun. 2008; 4097
    • 8h Akiyama T. Chem. Rev. 2007; 107: 5744
    • 8i Akiyama T, Itoh J, Fuchibe K. Adv. Synth. Catal. 2006; 348: 999

    • See also:
    • 8j Akiyama T, Mori K. Chem. Rev. 2015; 115: 9277
  • 9 Klussmann M, Ratjen L, Hoffmann S, Wakchaure V, Goddard R, List B. Synlett 2010; 2189

    • For selected examples of calcium phosphate salt, see:
    • 10a Lalli C, Dumoulin A, Lebée C, Drouet F, Guérineau V, Touboul D, Gandon V, Zhu J, Masson G. Chem. Eur. J. 2015; 21: 1704
    • 10b Nakamura S, Ohara M, Koyari M, Hayashi M, Hyodo K, Rashid Nabisaheb N, Funahashi Y. Org. Lett. 2014; 16: 4452
    • 10c Mao Z, Li W, Shi Y, Mao H, Lin A, Zhu C, Cheng Y. Chem. Eur. J. 2013; 19: 9754
    • 10d Rueping M, Bootwicha T, Kambutong S, Sugiono E. Chem. Asian J. 2012; 7: 1195
    • 10e Drouet F, Lalli C, Liu H, Masson G, Zhu J. Org. Lett. 2011; 13: 94
    • 10f Zhang Z, Zheng W, Antilla JC. Angew. Chem. Int. Ed. 2011; 50: 1135
    • 10g Zheng W, Zhang Z, Kaplan MJ, Antilla JC. J. Am. Chem. Soc. 2011; 133: 3339
    • 10h Hatano M, Moriyama K, Maki T, Ishihara K. Angew. Chem. Int. Ed. 2010; 49: 3823
  • 11 Cai Y, Liu X, Zhou P, Kuang Y, Lin L, Feng X. Chem. Commun. 2013; 49: 8054
  • 12 Qi J, Fan G.-T, Chen J, Sun M.-H, Dong Y.-T, Zhou L. Chem. Commun. 2014; 50: 13841
    • 13a Lebée C, Kataja A, Blanchard F, Masson G. Chem. Eur. J. 2015; 21: 8399
    • 13b Dumoulin A, Lalli C, Retailleau P, Masson G. Chem. Commun. 2015; 51: 5383
    • 13c Bernadat G, Masson G. Synlett 2014; 25: 2842
    • 13d Bekkaye M, Masson G. Org. Lett. 2014; 16: 1510
    • 13e Carboni A, Dagousset G, Magnier E, Masson G. Org. Lett. 2014; 16: 1240
    • 13f Bekkaye M, Su Y, Masson G. Eur. J. Org. Chem. 2013; 19: 3978
    • 13g He L, Laurent G, Retailleau P, Folléas B, Brayer J.-L, Masson G. Angew. Chem. Int. Ed. 2013; 52: 11088
    • 13h Courant T, Masson G. Chem. Eur. J. 2012; 18: 423
    • 13i Dagousset G, Zhu J, Masson G. J. Am. Chem. Soc. 2011; 133: 14804
    • 13j Liu H, Dagousset G, Masson G, Retailleau P, Zhu J. J. Am. Chem. Soc. 2009; 131: 4598
  • 14 Akiyama T. US 0276329 A1, 2006
    • 15a Nakatsuji H, Sawamura Y, Sakakura A, Ishihara K. Angew. Chem. Int. Ed. 2014; 53: 6974
    • 15b Sawamura Y, Nakatsuji H, Sakakura A, Ishihara K. Chem. Sci. 2013; 4: 4181
    • 15c Sakakura A, Ukai A, Ishihara K. Nature (London, U.K.) 2007; 445: 900

      For selected references on chiral phosphoric acid and phosphate-catalyzed enantioselective halogenation of olefins, see:
    • 16a Romanov-Michailidis F, Romanova-Michaelides M, Pupier M, Alexakis A. Chem. Eur. J. 2015; 21: 5561
    • 16b Müller CH, Rösner C, Hennecke U. Chem. Asian J. 2014; 9: 2162
    • 16c Liu H, Jiang G, Pan X, Wan X, Lai Y, Ma D, Xie W. Org. Lett. 2014; 16: 1908
    • 16d Xie W, Jiang G, Liu H, Hu J, Pan X, Zhang H, Wan X, Lai Y, Ma D. Angew. Chem. Int. Ed. 2013; 52: 12924
    • 16e Romanov-Michailidis F, Guénée L, Alexakis A. Angew. Chem. Int. Ed. 2013; 52: 9266
    • 16f Li G.-X, Fu Q.-Q, Zhang X.-M, Jiang J, Tang Z. Tetrahedron: Asymmetry 2012; 23: 245
    • 16g Honjo T, Phipps RJ, Rauniyar V, Toste FD. Angew. Chem. Int. Ed. 2012; 51: 9684
    • 16h Denmark SE, Burk MT. Org. Lett. 2012; 14: 256
    • 16i Huang D, Wang H, Xue F, Guan H, Li L, Peng X, Shi Y. Org. Lett. 2011; 13: 6350
    • 16j Rauniyar V, Lackner AD, Hamilton GL, Toste FD. Science 2011; 334: 1681
    • 16k Hennecke U, Müller CH, Fröhlich R. Org. Lett. 2011; 13: 860
    • 17a McNerny DQ, Mullen DG, Majoros IJ, Holl MM. B, Baker JR. Jr. Click Chemistry for Biotechnology and Materials Science. Lahann J. John Wiley and Sons; Chichester: 2009: 177
    • 17b Iha RK, Wooley KL, Nyström AM, Burke DJ, Kade MJ, Hawker CJ. Chem. Rev. 2009; 109: 5620
    • 17c Franc G, Kakkar AK. Chem. Soc. Rev. 2010; 39: 1536
  • 18 Representative Procedure for Iodoamination Reaction A flame-dried test tube, flushed with argon, was charged with enecarbamate 1a (38.2 mg, 0.2 mmol, 2.0 equiv) and catalyst 4a (3.8 mg, 0.005 mmol, 5 mol%) sequentially and dissolved in distilled toluene (0.4 mL). The reaction mixture is stirred at r.t. for 2 min before the addition of solid NIS (2b; 22.5 mg, 0.1 mmol, 1.0 equiv) and distilled toluene (0.6 mL). The resultant reaction mixture was stirred for 2 h at r.t. Then, the reaction mixture was directly purified by flash chromatography on silica gel (n-heptane–EtOAc = 7:3) to afford the corresponding pure iodoaminal 6a as a white solid (33 mg, isolated yield 78%); dr > 95:5; [α]D 23 –45.6 (c 0.9, CHCl3); mp 172–174 °C. 1H NMR (300 MHz, CDCl3): δ = 7.37–7.32 (m, 5 H), 6.00–5.92 (m, 2 H), 5.16–5.07 (m, 2 H), 4.74–4.63 (m, 1 H), 2.70 (s, 4 H), 1.96 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 176.3 (2 C), 154.9, 135.9, 128.8 (2 C), 128.6 (2 C), 128.5, 67.8, 64.6, 28.1 (2 C), 24.8, 23.3 ppm. IR (neat): ν = 2925, 1703, 1513, 1455, 1382, 1258, 1012, 793 cm–1. ESI-HRMS (positive): m/z calcd for C15H17IN2O4Na [M + Na]+: 439.0125; found: 439.0128. The ee is 99% determined by HPLC (AD-H, heptane–EtOH = 80:20, flow rate = 1.0 mL/min, 254 nm): t R (minor isomer) = 10.7 min; t R (major isomer) = 13.3 min.