Synlett 2020; 31(09): 899-902
DOI: 10.1055/s-0039-1690856
letter
© Georg Thieme Verlag Stuttgart · New York

O-Alkyl S-(Pyridin-2-yl)carbonothiolates: Operationally Simple and Highly Nitrogen-Selective Reagents for Alkoxy Carbonylation of Amino Groups

Tomoyuki Suzuki
,
Kosaku Tanaka III
,
Yoshimitsu Hashimoto
,
Nobuyoshi Morita
,
Osamu Tamura
This work was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant Number 17K0821 to O.T.).
Further Information

Publication History

Received: 09 January 2020

Accepted after revision: 26 February 2020

Publication Date:
13 March 2020 (online)


Abstract

Amino groups are selectively protected in good yields by reaction with O-alkyl S-(pyridin-2-yl)carbonothiolates in an appropriate solvent at room temperature in air. Even glucosamine, which contains multiple hydroxyl groups, is selectively N-protected in methanol.

Supporting Information

 
  • References and Notes

  • 1 Greene’s Protective Groups in Organic Synthesis. Wuts PG. M. John Wiley & Sons; Hoboken: 2014. Chap. 8

    • For a review, see:
    • 2a Subirós-Funosas R, Khattab SN, Nieto-Rodríguez L, El-Faham A, Albericio F. Aldrichimica Acta 2013; 46: 21

    • See also:
    • 2b Shimizu M, Sodeoka M. Org. Lett. 2007; 9: 5231
    • 2c Khattab SN, Subiós-Funosas R, El-Faham A, Albericio F. Tetrahedron 2012; 68: 3056
    • 2d Kumar A, Sharma A, Haimov E, El-Faham A, de la Torre BG, Albericio F. Org. Process Res. Dev. 2017; 21: 1533
    • 2e Du F, Zhou Q, Fu Y, Zhao H, Chen Y, Chen G. New J. Chem. 2019; 43: 6549
    • 2f Dobi Z, Reddy BN, Renders E, Van Raemdonck L, Mensch C, De Smet G, Chen C, Bheeter C, Sergeyev S, Herrebout WA, Maes BU. W. ChemSusChem 2019; 12: 3103
  • 3 Zeng R, Bao L, Sheng H, Sun L, Chen M, Feng Y, Zhu M. RSC Adv. 2016; 6: 78576
  • 4 Godoi M, Botteselle GV, Rafique J, Rocha MS. T, Pena JM, Braga AL. Asian J. Org. Chem. 2013; 2: 746
    • 5a Chankeshwara SV, Chakraborti AK. Org. Lett. 2006; 8: 3259
    • 5b Gawande MB, Branco PS. Green Chem. 2011; 13: 3355
    • 5c Giola ML, Gagliardi A, Leggio A, Leotta V, Romio E, Liguori A. RSC Adv. 2015; 5: 63407
    • 5d Ingale AP, More VK, Gangarde US, Shinde SV. New J. Chem. 2018; 42: 10142

      For a review, see:
    • 6a Mukaiyama T. Angew. Chem., Int. Ed. Engl. 1976; 15: 94

    • See also:
    • 6b Mukaiyama T, Matsueda R, Suzuki M. Tetrahedron Lett. 1970; 11: 1901
    • 6c Lloyd K, Young GT. J. Chem. Soc. C 1971; 2890
  • 7 Mukaiyama T, Araki M, Takei H. J. Am. Chem. Soc. 1973; 95: 4763
    • 8a Corey EJ, Nicolaou KC. J. Am. Chem. Soc. 1974; 96: 5614
    • 8b Corey EJ, Nicolaou KC, Melvin LS. Jr. J. Am. Chem. Soc. 1975; 97: 653
    • 8c Corey EJ, Nicolaou KC, Melvin LS. Jr. J. Am. Chem. Soc. 1975; 97: 654
    • 8d Barry CS, Bushby N, Charmant JP. H, Elsworth JD, Harding JR, Willis CL. Chem. Commun. 2005; 5097
    • 9a Hanessian S, Conde JJ, Lou B. Tetrahedron Lett. 1995; 36: 5865
    • 9b Hanessian S, Mascitti V, Rogel O. J. Org. Chem. 2002; 67: 3346
    • 9c Hanessian S, Wang X, Ersmark K, Del Valle JR, Klegraf E. Org. Lett. 2009; 11: 4232
  • 10 Muguruma K, Shirasaka T, Akiyama D, Fukumoto K, Taguchi A, Takayama K, Taniguchi A, Hayashi Y. Angew. Chem. Int. Ed. 2018; 57: 2170
    • 11a Kumar VP, Babu VS, Yahata K, Kishi Y. Org. Lett. 2017; 19: 2766
    • 11b Ai Y, Ye N, Wang O, Yahata K, Kishi Y. Angew. Chem. Int. Ed. 2017; 56: 10791
    • 11c Yahata K, Ye N, Ai Y, Iso K, Kishi Y. Angew. Chem. Int. Ed. 2017; 56: 10796
  • 12 Kim S, Lee JI, Yi KY. Bull. Chem. Soc. Jpn. 1985; 58: 3570
  • 13 Usami S, Suzuki T, Mano K, Tanaka K III, Hashimoto Y, Morita N, Tamura O. Synlett 2019; 30: 1561
  • 14 In addition to usual abbreviations for carbamates, Moc (methyloxycarbonyl) and Eoc (ethyloxycarbonyl) are used in this paper.
  • 15 Typical Procedure To a stirred solution of phenylalaninol (4, 53.0 mg, 0.350 mmol) in methanol (1 mL) was added dropwise a solution of 1d (121 mg, 0.422 mmol) in methanol (1 mL). After 10 min, completion of the reaction was confirmed by TLC. The mixture was concentrated in vacuo, and the residue was purified by column chromatography on silica gel (hexane–EtOAc, 5:1 to 2:1) to afford 5d (111 mg, 97%). IR (KBr): 3422, 2953, 1720, 1541, 1252, 1092 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.34–7.17 (5 H, m), 5.44 (1 H, br d, J = 8.4 Hz), 4.72 (1 H, d, J = 12.3 Hz), 4.66 (1 H, d, J = 12.3 Hz), 4.03–3.91 (1 H, m), 3.75–3.64 (1 H, m), 3.63–3.51 (1 H, m), 2.89 (2 H, d, J = 6.9 Hz), 2.52–2.38 (1 H, m). 13C NMR (75 MHz, CDCl3): δ = 154.5, 137.3, 129.2, 128.6, 126.7, 95.5, 74.4, 63.4, 54.2, 37.2. HRMS (ESI): m/z calcd for C12H14Cl3NNaO3 [M + Na]+: 347.9937; found: 347.9948.
  • 16 Under similar conditions using N-(2,2,2-trichloroethoxycarbonyloxy)succinimide (Troc-OSu) or 2,2-trichloroethoxycarbonyl chloride (TrocCl), 5d was obtained 93% or 27% yield, respectively.
  • 17 Pires RA, Abul-Haija YM, Costa DS, Novoa-Carballal R, Reis RL, Ulijn RV, Pashkuleva I. J. Am. Chem. Soc. 2015; 137: 576