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Synthesis 2013; 45(24): 3361-3368
DOI: 10.1055/s-0033-1339921
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© Georg Thieme Verlag Stuttgart · New York

SNAAP Sulfonimidate Alkylating Agent for Acids, Alcohols, and Phenols[1]

Tom J. Maricich*
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Matthew J. Allan
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Brett S. Kislin
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Andrea I-T. Chen
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Fan-Chun Meng
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Christine Bradford
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Nai-Chia Kuan
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Jeremy Wood
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Omonigho Aisagbonhi
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Alethea Poste
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Dustin Wride
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Sylvia Kim
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Therese Santos
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Michael Fimbres
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Dianne Choi
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Haydi Elia
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Joseph Kaladjian
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Ali Abou-Zahr
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
,
Arturo Mejia
Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840, USA   Fax: +1(562)9858557   Email: tom.maricich@csulb.edu
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Publication History

Received: 03 August 2013

Accepted after revision: 22 September 2013

Publication Date:
07 November 2013 (online)

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Abstract

Stable, crystalline ethyl N-tert-butyl-4-nitrobenzenesulfonimidate has been prepared in high yield by direct O-ethylation of N-tert-butyl-4-nitrobenzenesulfonamide with iodoethane and silver(I) oxide in dichloromethane. This sulfonimidate directly ethylates various acids to esters; the stronger the acid, the faster it alkylates and in higher yield. It readily ethylates alcohols and phenols to ethers at room temperature in the presence of tetrafluoroboric acid catalyst without molecular rearrangements or racemization. We have defined these reactions as SNAAP alkylations: [substitution, nucleophilic of acids, alcohols and phenols]. The hard sulfonimidate alkylating agent is chemoselective, preferring oxygen > nitrogen > sulfur. The sulfonamide byproduct of alkylation is readily recycled to the sulfonimidate.

Key words

mild alkylation - mild esterification - esters - ethers - sulfonimidate

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis. Included are copies of 1H and 13C NMR spectra of compounds 1 and 2 and of 1H spectra of ethylation products reported in this study.
  • Supporting Information