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.
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1.0 Introduction
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1.1 Metalation of Sulfonamides
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1. Intra/Inter-molecular Competition and Directing
Ability
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1.3 Metalating Bases
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1.4 Types of Sulfonamides
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2.0 Addition of Electrophiles to Metalated Sulfonamides
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2.1 Carbon Dioxide (CO)2 as an Electrophile
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2.2 Carbonyls as Electrophiles
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2.2.1 Ketones
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2.2.2 Aldehydes
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2.3 Benzonitrile as an Electrophile
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2.4 Phenyl Isocyanate as Electrophile
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2.5 Phenyl Thioisocyanates as Electrophiles
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2.6 Diethyloxalate [(CO2Et)2] as
Electrophile
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2.7 Oxiranes as Electrophiles
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2.8 N,N-Diethylcarbamoyl
Chloride as an Electrophile
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2.9 Ethyl Formate as an Electrophile
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2.10 Anhydrides as Electrophiles
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2.11 Alkylation of Sulfonamide Lithio Species
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2.12 Dimethylformamide (DMF) as an Electrophile
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2.13 Disulfides as Electrophiles
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2.14 Trimethylsilyl Chloride (TMSCl) as an Electrophile
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2.15 Introduction of Halogens
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2.15.1 Chlorides
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2.15.2 Bromides
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2.15.3 Iodine
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2.15.4 Fluorides
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2.16 Diethoxy Chlorophosphate as Electrophile
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2.17 Rearrangements in N-Phenyl-substituted
Sulfonamides
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2.18 Cross Coupling Reactions with Metalated Sulfonamides
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2.19 Formation of Phenols
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2.20 Unusual Reactions of Sulfonamides
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3.0 Applications of Metalated Sulfonamides in Synthesis
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3.1 Introduction
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3.2 Preparation of Sultams
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3.3 Preparation of Sultones
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3.4 Synthesis of Benzothiazinones
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3.5 Synthesis of Benzothiazepines
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3.6 Thiazocin-9,9-dioxides
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3.7 Synthesis of Pyridine Heterocycles
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3.8 Kinetic and Thermodynamic Stabilities of the
Sulfonamide
Lithio Species
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3.9 Synthesis of Ellipticine Analogues
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3.10 Synthesis of Tricyclic Benzothiazinones
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3.11 Introduction of the Sulfonamide Function by Metalation
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3.12 Preparation of 2-Benzothiazocine and 2-Benzothiazacyclopentadecine
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3.13 Synthesis of 2-Benzoxathiazonine-1,1-dione
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4.0 Conclusion
benzenesulfonamide - butyl lithium - Directed ortho Metalation (DoM) - Directed Metalation Group (DMG) - heterocycles
