Cleavage of sulfonamides with sodium naphthalene

Ji, Sungchul; Gortler, Leon B.; Waring, Anita J.; Battisti, Angello J.; Bank, Shelton; Closson, W. D.; Wriede, Peter A.

doi:10.1021/ja00996a055

Cited by 166 publications

(64 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The sulfonamide may then serve as a protecting group for the nitrogen atom during further synthetic manipulation. The use of sulfonamides as protecting groups in complex molecules was hindered by the harsh conditions 6 needed to remove the sulfonamide. The development of 2-(trimethylsilyl)-ethanesulfonamide (SES-NH 2 ) by Weinreb 7 and the implementation of 2- and 4-nitrobenzenesulfonamides by Fukuyama 8 have resulted in a greatly increased use of sulfonamides in organic synthesis, primarily because these sulfonamides are readily and reliably removed under mild conditions.…”

mentioning

confidence: 99%

“…7b,8a,12 Given the high level of interest in sulfonamides, it is perhaps unsurprising that new, more atom-economical catalytic methods for their formation have continued to evolve. Many of these methods employ transition metal catalysts, including the hydroaminations of alkenes, 13 C-H activation methods, 14 metal catalyzed additions to N-sulfonyl imines, 6b,15 alkylation via π-allyl metal complexes, 16 and alkylation of alcohols via borrowing hydrogen methods. 17 Direct alkylation of benzylic and allylic alcohols and ethers has also been explored, 18 although these methods typically require the use of strong Brønsted or Lewis acids and elevated temperatures.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions

Wallach

Chisholm

2016

J. Org. Chem.

View full text Add to dashboard Cite

An intermolecular alkylation of sulfonamides with trichloroacetimidates is reported. This transformation does not require an exogenous acid, base, or transition metal catalyst, instead the addition occurs in refluxing toluene without additives. The sulfonamide alkylation partner appears to be only limited by sterics, with unsubstituted sulfonamides providing better yields than more encumbered N-alkyl sulfonamides. The trichloroacetimidate alkylating agent must be a stable cation precursor for the substitution reaction to proceed under these conditions. Graphical abstractThe sulfonamide functional group has played an important role in the development of numerous pharmaceuticals. While best known as antibiotics, sulfonamide scaffolds provide a diverse range of biological activity including antitumor, antiviral, diuretic, antiinflammatory and anti-hypertensive properties. 1 Summaries of the top selling pharmaceuticals clearly demonstrate that sulfonamides are well represented in these valuable structures. 2 Data on recently approved pharmaceuticals indicate that sulfonamides continue to be popular in drug discovery, 3 with recent publications in the medicinal chemistry field corroborating that the investigation of sulfonamide-containing structures is ongoing. 4 Sulfonamides also have proven useful in agricultural and insecticidal applications. 5

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions

Wallach

Chisholm

2016

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…Upon treatment with sodium naphthalenide (THF, À78 8C), compound 30 was cleanly converted to the free secondary amine 31 (75 %). [44] Alternatively, protection of the 1,2-diol 25' as an acetonide 32 (97 %) and subsequent reductive cleavage of the tosyl group provided secondary amine 33 in good yield (77 %; Scheme 12).…”

Section: 2-diastereoselectivity Of the Wittig Rearrangement Of A-almentioning

confidence: 99%

Synthesis of 1,2‐Amino Alcohols by Sigmatropic Rearrangements of 3‐(N‐Tosylamino)allylic Alcohol Derivatives

Barbazanges

Meyer

Cossy

et al. 2011

Chemistry A European J

View full text Add to dashboard Cite

Sigmatropic rearrangements of 3-(N-tosylamino)allylic alcohol derivatives, a particular subclass of functionalized enamides, have been investigated. Whereas the presence of the nitrogen atom alters the stereochemical outcome of Ireland-Claisen rearrangements of glycolates derived from such substrates, [2,3]-Wittig rearrangements of α-allyloxy acetamides or propargylic ethers derivatives provide access to a wide variety of functionalized 1,2-amino alcohols usually with high levels of stereocontrol, as well as to heterocyclic compounds. The stereoselectivity issues of these rearrangements (1,2-diastereoselectivity, auxiliary-induced diastereoselection, chirality transfer, and double stereodifferentiation) were thoroughly investigated.

show abstract

“…We found that both the conversion and the ee decreased at a lower hydrogen pressure ( [15][16][17][18].…”

mentioning

confidence: 99%

A Highly Enantioselective, Pd–TangPhos‐Catalyzed Hydrogenation of N‐Tosylimines

et al. 2006

View full text Add to dashboard Cite

Although significant progress has been made in the catalytic asymmetric reduction of ketones and olefins over the last few decades, [1] the asymmetric reduction of imines remains a major challenge.[2] Enantioselective reductive amination with organocatalysts has recently been reported, [3] and a number of transition-metal-based catalysts, such as those containing Rh, [4] Ru, [5] Ti, [6] Zr, [6d] and Ir, [7] have been applied to the asymmetric hydrogenation of imines. However, this method has been less successful than the hydrogenation of other substrates. The main obstacles in solving the problems in this hydrogenation approach include different enantioselectivities for E and Z isomers of acyclic imines, [6b,c, 8] the instability of some imines prepared from ketones, and the inhibitory effect of the amine products on the metal catalysts. In order to solve these problems, N-tosylimines were selected as the hydrogenation substrates since they are relatively stable and can be easily obtained from the corresponding ketones exclusively as the E isomer. [9] In addition, the strongly electron-withdrawing character of the tosyl group reduces the inhibitory effect of the reduction product on the catalysts, which might lead to higher reactivity. These advantages of N-tosylimines as substrates prompted us to look for a good reduction catalyst for the substrates. To the best of our knowledge, the asymmetric hydrogenation of N-tosylimines has rarely been explored, and the best result reported so far is the 84 % ee reported by the Charette group using a Ru-Binap catalyst. [9] In our search for effective hydrogenation catalysts for the reduction of N-tosylimines, we have explored this trans-

show abstract

Cleavage of sulfonamides with sodium naphthalene

Cited by 166 publications

References 2 publications

Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions

Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions

Synthesis of 1,2‐Amino Alcohols by Sigmatropic Rearrangements of 3‐(N‐Tosylamino)allylic Alcohol Derivatives

A Highly Enantioselective, Pd–TangPhos‐Catalyzed Hydrogenation of N‐Tosylimines

Contact Info

Product

Resources

About