CC BY-ND-NC 4.0 · SynOpen 2019; 03(01): 21-25
DOI: 10.1055/s-0037-1611722
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A Concise, Catalyst-Free Synthesis of Davis’ Oxaziridines using Sodium Hypochlorite

Saori Kitagawa
a  Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara.masayuki@sist.ac.jp
,
Hiromitsu Mori
a  Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara.masayuki@sist.ac.jp
,
Tatsuya Odagiri
b  R&D Department of Chemicals, Nippon Light Metal Company, Ltd., Kambara, Shimizu-ku, Shizuoka 421-3203, Japan
,
Katsuya Suzuki
a  Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara.masayuki@sist.ac.jp
,
You Kikkawa
a  Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara.masayuki@sist.ac.jp
,
Rie Osugi
a  Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara.masayuki@sist.ac.jp
,
c  The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047, Japan
,
d  Research and Development Department, Iharanikkei Chemical Industry Co. Ltd., Kambara, Shimizu-ku, Shizuoka 421-3203, Japan
,
a  Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara.masayuki@sist.ac.jp
› Author Affiliations
This work was performed under the Cooperative Research Program of the ‘Network Joint Research Center for Materials and Devices’.
Further Information

Publication History

Received: 15 December 2018

Accepted after revision: 23 January 2019

Publication Date:
19 February 2019 (online)

Abstract

N-Sulfonyloxaziridines (Davis’ oxaziridines) can be synthesized by reacting the corresponding N-sulfonylimines with aqueous sodium hypochlorite in acetonitrile without any catalyst. The pH of the aqueous sodium hypochlorite is crucial to obtain the product in high yield. Optimized conditions are presented that allow synthetically useful Davis’ oxaziridines to be easily obtained in up to 90% yields from the corresponding imines by using inexpensive, stable, environmentally friendly sodium hypochlorite pentahydrate crystals as the oxidant, with high reproducibility.

 
  • References and Notes


    • For recent reviews, see:
    • 1a Williamson KS, Michaelis DJ, Yoon TP. Chem. Rev. 2014; 114: 8016
    • 1b Sala GD, Lattanzi A. ACS Catal. I 2014; 4: 1234
    • 2a Davis FA, Stringer OD. J. Org. Chem. 1982; 47: 1774
    • 2b Davis FA, Chattopadhyay S, Towson JC, Lal S, Reddy T. J. Org. Chem. 1988; 53: 2087
    • 2c Davis FA, Towson JC, Weismiller MC, Lal S, Carroll PJ. J. Am. Chem. Soc. 1988; 110: 8477
    • 2d Davis FA, Sheppard AC, Chen B, Haque MS. J. Am. Chem. Soc. 1990; 112: 6679
    • 2e Davis FA, Weismiller MC. J. Org. Chem. 1990; 55: 3715
    • 2f Davis FA, Sheppard AC. Tetrahedron 1989; 45: 5703
    • 2g Davis FA, Chen BC. Chem. Rev. 1992; 92: 919
    • 2h Petrov VA, Resnati G. Chem. Rev. 1996; 96: 1809
    • 2i Narasaka K, Ukaji Y, Watanabe K. Bull Chem. Soc. Jpn. 1987; 96: 1457

      Asymmetric syntheses of oxaziridines:
    • 3a Takizawa S, Kishi K, Abozeid MA, Murai K, Fujioka H, Sasaia H. Org. Biomol. Chem. 2016; 14: 761
    • 3b Lykke L, Rodríguez-Escrich C, Jørgensen KA. J. Am. Chem. Soc. 2011; 133: 14932
    • 3c Zhang T, He W, Zhao X, Jin Y. Tetrahedron 2013; 69: 7416
    • 3d Jin Y, Zhang T, Zhang W, Chang S, Feng B. Chirality 2014; 26: 150
    • 3e Uraguchi D, Tsutsumi R, Ooi T. J. Am. Chem. Soc. 2013; 135: 8161
    • 3f Tsutsumi R, Kim S, Uraguchi D, Ooi T. Synthesis 2014; 871
    • 3g Uraguchi D, Tsutsumi R, Ooi T. Tetrahedron 2014; 70: 1691
    • 3h Olivares-Romero JL, Li Z, Yamamoto H. J. Am. Chem. Soc. 2012; 134: 5440
  • 4 Galvin JM, Jacobsen EN, Palucki M, Frederick MO. e-EROS 2013; DOI: 10.1002/047084289X.rs084.pub3. ; and references cited therein
    • 5a Kirihara M, Okada T, Sugiyama Y, Akiyoshi M, Matsunaga T, Kimura Y. Org. Process Res. Dev. 2017; 21: 1925
    • 5b Okada T, Asawa T, Sugiyama Y, Kirihara M, Iwai T, Kimura Y. Synlett 2014; 25: 596
    • 5c Okada T, Asawa T, Sugiyama Y, Iwai T, Kirihara M, Kimura Y. Tetrahedron 2016; 72: 2818
    • 5d Okada T, Matsumuro H, Kitagawa S, Iwai T, Yamazaki K, Kinoshita Y, Kimura Y, Kirihara M. Synlett 2015; 26: 2547
    • 5e Okada T, Matsumuro H, Iwai T, Kitagawa S, Yamazaki K, Akiyama T, Asawa T, Sugiyama Y, Kimura Y, Kirihara M. Chem. Lett. 2015; 44: 185
  • 6 Given that addition of 10 mol% tetrabutylammonium hydroxide (Bu4NOH) accelerated the oxidation reaction in a biphasic solvent system using trifluoromethylbenzene (benzotrifluoride, BTF), the reaction might proceed enantioselectively if an optically pure alkylammonium salt was employed. As a preliminary result, the desired product 2a was obtained with 7% ee when the reaction was conducted using N-benzylcinchonidinium chloride.