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Synlett 2002(8): 1181-1210
DOI: 10.1055/s-2002-32945
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Metalated Sulfonamides and their Synthetic Applications

Oluwole Babafemi Familoni*
Department of Chemistry, University of Lagos, Akoka - Yaba, Lagos, Nigeria
Fax: +234(1)2690717; e-Mail: familoni@unilag.edu;
Further Information

Publication History

Received 13 August 2001
Publication Date:
25 July 2002 (online)

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Abstract

Benzenesulfonamide is a powerful Directed Metalation Group (DMG) whose great potentials are yet to be fully explored. This account highlights some of the vast possibilities inherent in arylsulfonamides using the Directed ortho Metalation (DoM) methodology. It shows some of the products of metalation and their applications in heterocyclic synthesis. Concomitant rearrangements and new developments are also presented.

  • 1.0 Introduction

  • 1.1 Metalation of Sulfonamides

  • 1. Intra/Inter-molecular Competition and Directing Ability

  • 1.3 Metalating Bases

  • 1.4 Types of Sulfonamides

  • 2.0 Addition of Electrophiles to Metalated Sulfonamides

  • 2.1 Carbon Dioxide (CO)2 as an Electrophile

  • 2.2 Carbonyls as Electrophiles

  • 2.2.1 Ketones

  • 2.2.2 Aldehydes

  • 2.3 Benzonitrile as an Electrophile

  • 2.4 Phenyl Isocyanate as Electrophile

  • 2.5 Phenyl Thioisocyanates as Electrophiles

  • 2.6 Diethyloxalate [(CO2Et)2] as Electrophile

  • 2.7 Oxiranes as Electrophiles

  • 2.8 N,N-Diethylcarbamoyl Chloride as an Electrophile

  • 2.9 Ethyl Formate as an Electrophile

  • 2.10 Anhydrides as Electrophiles

  • 2.11 Alkylation of Sulfonamide Lithio Species

  • 2.12 Dimethylformamide (DMF) as an Electrophile

  • 2.13 Disulfides as Electrophiles

  • 2.14 Trimethylsilyl Chloride (TMSCl) as an Electrophile

  • 2.15 Introduction of Halogens

  • 2.15.1 Chlorides

  • 2.15.2 Bromides

  • 2.15.3 Iodine

  • 2.15.4 Fluorides

  • 2.16 Diethoxy Chlorophosphate as Electrophile

  • 2.17 Rearrangements in N-Phenyl-substituted Sulfonamides

  • 2.18 Cross Coupling Reactions with Metalated Sulfonamides

  • 2.19 Formation of Phenols

  • 2.20 Unusual Reactions of Sulfonamides

  • 3.0 Applications of Metalated Sulfonamides in Synthesis

  • 3.1 Introduction

  • 3.2 Preparation of Sultams

  • 3.3 Preparation of Sultones

  • 3.4 Synthesis of Benzothiazinones

  • 3.5 Synthesis of Benzothiazepines

  • 3.6 Thiazocin-9,9-dioxides

  • 3.7 Synthesis of Pyridine Heterocycles

  • 3.8 Kinetic and Thermodynamic Stabilities of the
    Sulfonamide Lithio Species

  • 3.9 Synthesis of Ellipticine Analogues

  • 3.10 Synthesis of Tricyclic Benzothiazinones

  • 3.11 Introduction of the Sulfonamide Function by Metalation

  • 3.12 Preparation of 2-Benzothiazocine and 2-Benzothiazacyclopentadecine

  • 3.13 Synthesis of 2-Benzoxathiazonine-1,1-dione

  • 4.0 Conclusion

Key words

benzenesulfonamide - butyl lithium - Directed ortho Metalation (DoM) - Directed Metalation Group (DMG) - heterocycles

27

Familoni, O. B. In Practical DoM; Snieckus, V. Ed.;
In press.

53

Familoni, O. B. 1988, Unpublished results.