SelectiveOrthoand Benzylic Functionalization of Secondary and Tertiaryp-Tolylsulfonamides.Ipso-Bromo Desilylation and Suzuki Cross-Coupling Reactions

MacNeil, Stephen L.; Familoni, Oluwole B.; Snieckus, Victor

doi:10.1021/jo001402s

Cited by 63 publications

(25 citation statements)

References 29 publications

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“…In addition, we would like to explore the possibility of using the sulfonyl groups at the 2,2Ј-positions as the directing groups for the functionalization of the 3,3Ј-positions by ortho-lithiation. [8] Resulting dihalide 1e could then serve as a common precursor for a series of 3,3Ј-substituted CSIs. Our approach should provide a more general and convergent synthesis to a wide variety of CSIs with different substituents at the 3,3Ј-positions by using dihalide 1e as the common starting material.…”

Section: Resultsmentioning

confidence: 99%

“…It has been reported that the sulfonamide group could serve as a director for ortholithiation in an aromatic system. [8] However, direct lithiation of N-substituted 1d with various organolithium reagents was not successful. The major products were the ringopened products of the sulfonimide, even when a bulky reagent such as tert-butyllithium was used.…”

Section: Resultsmentioning

confidence: 99%

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Practical Synthetic Approach to Chiral Sulfonimides (CSIs) – Chiral Brønsted Acids for Organocatalysis

Chen

Wong

et al. 2010

Eur J Org Chem

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Practical Synthetic Approach to Chiral Sulfonimides (CSIs) – Chiral Brønsted Acids for Organocatalysis

Chen

Wong

et al. 2010

Eur J Org Chem

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“…McNeil et al 43 smoothly obtained 2-substituted secondary and tertiary sulfonamides in 78-92% yields using iodine as electrophile by quenching the lithio species at both temperatures of -78°C and 0°C (Scheme 62).…”

Section: Scheme 61mentioning

confidence: 99%

Metalated Sulfonamides and their Synthetic Applications

Familoni¹

2002

Synlett

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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.3.12 Preparation of 2-Benzothiazocine and 2-Benzothiazacyclopentadecine 3.13 Synthesis of 2-Benzoxathiazonine-1,1-dione 4.0 Conclusion

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“…Aromatic sulfonamides, in turn, were obtained in a three-step procedure starting from commercially available benzenesulfonyl chloride. Ethyl and benzyl groups were introduced in ortho position via metallation-alkylation [13] and Negishi cross-coupling [14], respectively, starting from N-(tert-butyl)benzenesulfonamide (2) [15] ( 3 3a and 3b, resp. ; Scheme 2).…”

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confidence: 99%

Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes

Fruit

Müller

2004

Helvetica Chimica Acta

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Enantioselective intramolecular amidation of aliphatic sulfonamides was achieved for the first time by means of chiral carboxylatodirhodium(II) catalysts in conjunction with PhI(OAc) 2 and MgO in high yields and with enantioselectivities of up to 66% (Scheme 3, Table 1 isoquinoline-2-acetato). In addition, these carboxylatodirhodium(II) catalysts were also efficient in intramolecular amidations of aliphatic sulfamates esters, although the enantioselectivity of these latter reactions was significantly lower (Scheme 4, Table 3).Introduction. ± Amidation of saturated CÀH bonds and aziridination of olefins catalyzed by metal complexes based on Fe, Mn, Ru, Cu, or Rh are established methodologies for CÀN bond-formation [1] and, consequently, for the synthesis of amine derivatives. Some years ago, the Rh II -catalyzed aziridination [2] and sulfonamidation [3] with phenyliodinanes derived from aromatic sulfonamides has been investigated in our group. The reactions exhibited features analogous to the corresponding metal-catalyzed carbene-transfer reactions [4]. The aziridination was found to be stereospecific, except in the case of stilbene, and the amidation proceeded with retention of configuration at the reacting C-atom, indicating intervention of a metal-complexed nitrene, in analogy to the corresponding intermediate metallocarbenes resulting from decomposition of diazo compounds with Rh II catalysts. Some preliminary experiments showed that the system was suitable for asymmetric nitrene transfer. However, it suffered several shortcomings. Owing to the requirement of aromatic sulfonamides as precursors for the phenyliodinanes [5], the possibilities of carrying out intramolecular aziridinations and/or amidations [6] appeared very limited. In addition, a large excess of substrate was necessary in the case of intermolecular reactions to achieve satisfactory yields, while reactions carried out with an excess of reagent over the substrate produced unsatisfactory results. Finally, some reactions, in particular intermolecular amidations, proceeded very sluggishly and resulted in decomposition of the phenyliodinanes to afford sulfonamides without generation of the expected products of nitrene insertion.The transition-metal-catalyzed nitrene transfer has been further developed by other groups. Dodd, Dauban, and co-workers reported that, contrary to the traditional opinion [7], phenyliodinanes derived from aliphatic sulfonamides are isolable and may be used for nitrene-transfer reactions [8]. In addition, they found conditions allowing

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SelectiveOrthoand Benzylic Functionalization of Secondary and Tertiaryp-Tolylsulfonamides.Ipso-Bromo Desilylation and Suzuki Cross-Coupling Reactions

Cited by 63 publications

References 29 publications

Practical Synthetic Approach to Chiral Sulfonimides (CSIs) – Chiral Brønsted Acids for Organocatalysis

Practical Synthetic Approach to Chiral Sulfonimides (CSIs) – Chiral Brønsted Acids for Organocatalysis

Metalated Sulfonamides and their Synthetic Applications

Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes

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