Metal-Free Approach for the Synthesis of <i>N</i>-Aryl Sulfoximines via Aryne Intermediate

Aithagani, Sravan Kumar; Dara, Saidulu; Munagala, Gurunadham; Aruri, Hariprasad; Yadav, Mahipal; Sharma, Shweta; Vishwakarma, Ram A.; Singh, Parvinder Pal

doi:10.1021/acs.orglett.5b02804

Cited by 59 publications

(26 citation statements)

References 45 publications

(13 reference statements)

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“…The reaction was tolerant of substituted benzyne intermediates and extended aryl units, giving rise to arylated products 28 and 13 , respectively. 28 Moreover, trapping of an indolyne intermediate delivered heterocycle-containing product 14 . When applied to non-aromatic, strained alkynes, the methodology provided alkenylated products in good yields and stereoselectivities.…”

Section: Resultsmentioning

confidence: 99%

Arynes and Cyclic Alkynes as Synthetic Building Blocks for Stereodefined Quaternary Centers

et al. 2018

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We report a facile method to synthesize stereodefined quaternary centers from reactions of arynes and related strained intermediates using β-ketoester-derived substrates. The conversion of β-ketoesters to chiral enamines is followed by reaction with in situ generated strained arynes or cyclic alkynes. Hydrolytic workup provides the arylated or alkenylated products in enantiomeric excesses as high as 96%. We also describe the one-pot conversion of a β-ketoester substrate to the corresponding enantioenriched α-arylated product. Computations show how chirality is transferred from the N-bound chiral auxiliary to the final products. These are the first theoretical studies of aryne trapping by chiral nucleophiles to set new stereocenters. Our approach provides a solution to the challenging problem of stereoselective β-ketoester arylation/alkenylation, with formation of a quaternary center.

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Section: Resultsmentioning

confidence: 99%

Arynes and Cyclic Alkynes as Synthetic Building Blocks for Stereodefined Quaternary Centers

et al. 2018

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“…reported that N‐arylsulfoximines exhibited interesting physicochemical properties and in vitro characteristics [6] of great significance for drug development. Many N‐arylation substrates for NH‐sulfoximines have been identified, with examples of such substrates including aryl halides, [56] arylboronic acids, [57,58] aryl sulfonates, [59] arylsiloxanes, [60] aromatics, [65] aryl iodonium salts, [61] and others [62,63]…”

Section: Transformations Of Sulfoximinesmentioning

confidence: 99%

“…A set of metal‐free easy‐to‐operate N‐arylations of NH‐sulfoximines with benzyne precursors was reported in 2015 (Scheme 33). These N‐arylations with benzyne precursors were triggered with KF, and thus no transition metal catalyst was needed, [65] but benzyne precursors are expensive and difficult to prepare. This method could also provide chiral N‐arylsulfoximines.…”

Section: Transformations Of Sulfoximinesmentioning

confidence: 99%

Syntheses and Transformations of Sulfoximines

Zheng

Chen

Feng

et al. 2020

The Chemical Record

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Sulfoximines are widely used as medicines, agricultural chemicals, chiral precursors, and chiral ligands in asymmetric synthesis, as well as pivotal intermediates for the construction of heterocyclic compounds. NH‐sulfoximines may be synthesized from thioethers, sulfoxides, sulfilimines, and sulfinamides. NH‐sulfoximines can undergo various transformations, such as arylations, alkylations, vinylations, and alkynylations. Here, we review the methods that have been applied to the syntheses and transformations of NH‐sulfoximines.

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“…We reasoned however, that if this limitation could be overcome, a general method could be developed for the synthesis of enantioenriched N-H sulfoximines. Since a number of methods exist for the functionalisation of these derivatives via alkylation, arylation, acylation and sulfonylation, [43][44][45][46][47][48][49][50][51][52][53][54] N-H sulfoximines are a versatile and sought-after synthetic intermediate for the synthesis of numerous sulfoximine derivatives.…”

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confidence: 99%

General Method for the Asymmetric Synthesis of N–H Sulfoximines via C–S Bond Formation

et al. 2020

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A versatile method for the synthesis of enantioenriched N-H sulfoximines is reported. The approach stems from the organomagnesium-mediated ring opening of novel cyclic sulfonimidate templates. The reactions proceed in high yield and with excellent stereofidelity with alkyl, aryl and heteroaryl Grignard reagents. The chiral auxillary is readily removed from the resultant sulfoximines via an unusual oxidative debenzylation protocol that utilises molecular oxygen as the terminal oxidant. This provides a general strategy for the synthesis of highly enantioenriched N-H sulfoximines.Scheme 3. Oxidative debenzylation to yield enantioenriched N-H sulfoximines.

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Metal-Free Approach for the Synthesis of N-Aryl Sulfoximines via Aryne Intermediate

Cited by 59 publications

References 45 publications

Arynes and Cyclic Alkynes as Synthetic Building Blocks for Stereodefined Quaternary Centers

Arynes and Cyclic Alkynes as Synthetic Building Blocks for Stereodefined Quaternary Centers

Syntheses and Transformations of Sulfoximines

General Method for the Asymmetric Synthesis of N–H Sulfoximines via C–S Bond Formation

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