Reactions of Alkanesulfonyl Chlorides with Ketene N,N- and O,N-Acetals

Hasek, Robert H.; Meen, R. H.; Martin, J. C.

doi:10.1021/jo01016a037

Cited by 21 publications

(10 citation statements)

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“…Thietan-3-one-1,1-dioxide 286 can also occur in its enolic form 287 . However, NMR and IR data obtained from this compound in deuterium oxide, tetrachloroethane, or dimethyl sulfoxide showed no evidence for this tautomerism. , The occurrence of the enolic form in substituted thietan-3-ones-1,1-dioxides has been reported. , …”

Section: The Chemistry Of Thietan-3-onesmentioning

confidence: 80%

“…Reaction of phenylmethanesulfonyl chloride with [(1-ethoxy-2-methyl-1-propenyl)oxy]trimethylsilane and subsequent hydrolysis gave the thietan-3-one-1,1-dioxide 301 (R 1 , R 2 = CH 3 ; R 3 = H, R 4 = C 6 H 5 ) . The hydrolysis of 3-(dialkylamino)thiete-1,1-dioxides 302 also resulted in the formation of the corresponding thietan-3-one-1,1-dioxides 303 . − ,− The 3-dialkylaminothiete-1,1-dioxides 302 were obtained from the cycloaddition of alkylsulfonyl chlorides and ketene O,N-acetals or aminals 180-183,209 or from the cycloaddition of alkylsulfonyl chlorides and alkynylamines . Many different compounds 302 have been synthesized in this way.…”

Section: A Synthetic Methods For Thietan-3-onesa1 Synthesis From Acyc...mentioning

confidence: 99%

“…However, NMR and IR data obtained from this compound in deuterium oxide, tetrachloroethane, or dimethyl sulfoxide showed no evidence for this tautomerism. 180,181 The occurrence of the enolic form in substituted thietan-3-ones-1,1-dioxides has been reported. 182,183 This chapter will consist of two parts that will deal with the synthesis of this small sulfur-containing heterocycle and with further chemical transformations, respectively.…”

Section: The Chemistry Of Thietan-3-onesmentioning

confidence: 99%

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The Chemistry of Azetidin-3-ones, Oxetan-3-ones, and Thietan-3-ones

et al. 2001

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I. Introduction 29 II. The Chemistry of Azetidin-3-ones 29 A. Structural Data 29 B. Synthetic Methods for Azetidin-3-ones 31 B.1. Carbonyl Group Generation in the Azetidine Ring 31 B.2. Intramolecular Cyclization Reactions 34 B.3. 1,3-Dipolar Cycloaddition Reactions 36 C. Chemical Properties of Azetidin-3-ones 37 C.1. Transformations of the Carbonyl Group 37 C.2. Condensation Reactions − Synthesis of 2-Benzylideneazetidin-3-ones 40 C.3. Ring Transformations of Azetidin-3-ones 40 C.4. Miscellaneous 41 III. The Chemistry of Oxetan-3-ones 42 A. Structural Data 42 B. Synthetic Methods for Oxetan-3-ones 43 B.1. Decomposition of Diazoketones 43 B.2. Oxidation Reactions 44 B.3. Intramolecular Displacement Reactions 46 B.4. Miscellaneous 47 C. Chemical Properties of Oxetan-3-ones 48 C.1. Ring Opening and Ring Expansion of Oxetan-3-ones 48 C.2. Transformations of the Carbonyl Group 49 IV. The Chemistry of Thietan-3-ones 50 A. Synthetic Methods for Thietan-3-ones 51 A.1. Synthesis from Acyclic Precursors 51 A.2. Synthesis by Ring Transformations 53 B. Chemical Properties of Thietan-3-ones 54 B.1. Transformations of the Carbonyl Group 55 B.2. Aldol Reactions 56 B.3. Ring Transformations 56 V. Acknowledgments 58 VI. References 58

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Section: The Chemistry Of Thietan-3-onesmentioning

confidence: 80%

Section: A Synthetic Methods For Thietan-3-onesa1 Synthesis From Acyc...mentioning

confidence: 99%

Section: The Chemistry Of Thietan-3-onesmentioning

confidence: 99%

See 1 more Smart Citation

The Chemistry of Azetidin-3-ones, Oxetan-3-ones, and Thietan-3-ones

et al. 2001

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“…Unfortunately, β-alkyl-substituted and terminal ynamides were not applicable in this process (2e'-2f'). Since the aminocontaining full-substituted thiete sulfones are synthetically challenging 66 , this skeletal reorganization of ynamides provides a robust and efficient approach toward these molecules with the achievement of structural diversity and molecule complexity. Next, the scope for another skeletal reorganization toward propargyl sulfonamide was also investigated.…”

Section: E N D O -mentioning

confidence: 99%

Skeletal reorganization divergence of N-sulfonyl ynamides

Zeng

Lin

et al. 2020

Nat Commun

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Skeletal reorganization is a type of intriguing processes because of their interesting mechanism, high atom-economy and synthetic versatility. Herein, we describe an unusual, divergent skeletal reorganization of N-sulfonyl ynamides. Upon treatment with lithium diisopropylamine (LDA), N-sulfonyl ynamides undergo a skeletal reorganization to deliver thiete sulfones, while the additional use of 1,3-dimethyl-tetrahydropyrimidin-2(1H)-one (DMPU) shifts the process to furnish propargyl sulfonamides. This skeletal reorganization divergence features broad substrate scope and scalability. Mechanistically, experimental and computational studies reveal that these processes may initiate from a lithiation/4-exo-dig cyclization cascade, and the following ligand-dependent 1,3-sulfonyl migration or β-elimination would control the chemodivergence. This protocol additionally provides a facile access to a variety of privileged molecules from easily accessible ynamides.

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“…For example, the TIPSsubstituted ynamide 1e' could reorganize to product 2c' in 70% yield with retention of TIPS group, while the TMS-substituted ynamide 1f' could transformed to product 2d' in a remarkable 94% yield accompanied with TMS desilylation. Since the amino-containing full-substituted thiete sulfones are synthetically challenging 66 , this skeletal reorganization of ynamides provides a robust and efficient approach toward these molecules with the achievement of structural diversity and molecule complexity. Synthetic applications and mechanism study.…”

Section: Reaction Optimizationmentioning

confidence: 99%

Skeletal Reorganization Divergence of N-Sulfonyl Ynamides

Zeng

Lin

et al. 2020

Preprint

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Skeletal reorganization is a type of intriguing processes for their interesting mechanism, high atom-economy and synthetic versatility. Herein, we describe an unusual skeletal reorganization divergence of N-sulfonyl ynamides. Upon treatment with lithium diisopropylamine (LDA), the N-sulfonyl ynamides could undergo a skeletal reorganization to deliver thiete sulfones, while the additional use of DMPU would shift the process to furnish propargyl sulfonamides. Mechanistically, these processes are proposed to initiate from a lithiation/cyclization cascade, and the following ligand-dependent 1,3-sulfonyl migration or β-elimination would constitute the divergence. Therefore, this protocol not only represents a new skeletal reorganization mode, but also provides a facile access to privileged molecules from the easily accessible ynamides.

show abstract

Reactions of Alkanesulfonyl Chlorides with Ketene N,N- and O,N-Acetals

Cited by 21 publications

References 0 publications

The Chemistry of Azetidin-3-ones, Oxetan-3-ones, and Thietan-3-ones

The Chemistry of Azetidin-3-ones, Oxetan-3-ones, and Thietan-3-ones

Skeletal reorganization divergence of N-sulfonyl ynamides

Skeletal Reorganization Divergence of N-Sulfonyl Ynamides

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