Alkali Metals in Silica Gel (M-SG): A New Reagent for Desulfonation of Amines

Nandi, Partha; Redko, Mikhail Y.; Petersen, Kathryn; Dye, James; Lefenfeld, Michael; Vogt, Paul F.; Jackson, James E.

doi:10.1021/ol8021337

Cited by 59 publications

(34 citation statements)

References 48 publications

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“…Efforts have also been made to develop new and efficient methods for desulfonylation of conventional benzene-and p-toluenesulfonamides under milder conditions than the classical conditions. Several reagents such as Bu 3 SnH/AIBN, 11 SmI 2 , 12 TMSI, 13 TiCl 4 /Zn, 11b TiCl 4 /mischmetal, 14 TiCl 3 /Li, 15 Mg/MeOH, 16 Me 3 CoLi, Me 3 FeLi and Me 3 MnLi with Mg, 17 Ni(0)acac/i-PrMgCl, 18 photolysis, 19 TBAF, 20 phase-transfer catalyst, 21 alkali metals on silica gel, 22 and microwave irradiation in the presence of acid 23 were found to be applicable for desulfonylation. However, many of these reagents were effective only for arenesulfonamides having an activating group such as a phenyl, acyl, and Boc group on nitrogen, and were ineffective for stable amides such as N,N-dialkyltosylamides.…”

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confidence: 99%

Hg cathode-free electrochemical detosylation of N,N-disubstituted p-toluenesulfonamides: mild, efficient, and selective removal of N-tosyl group

Senboku

Nakahara

Fukuhara

et al. 2010

Tetrahedron Letters

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confidence: 99%

Hg cathode-free electrochemical detosylation of N,N-disubstituted p-toluenesulfonamides: mild, efficient, and selective removal of N-tosyl group

Senboku

Nakahara

Fukuhara

et al. 2010

Tetrahedron Letters

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“…The N-Ts group of the products can easily be removed [6] to afford the corresponding (aminoalkyl)naphthalenols, which can be utilized to prepare their various derivatives.…”

Section: C-nmr and Esi- And Hr-esi-ms)mentioning

confidence: 99%

An Efficient Synthesis of [(Tosylamino)alkyl]naphthalenols by Nucleophilic Addition of Naphthalen‐2‐ol with N‐Tosyl Imines Using Boron Trifluoride Etherate as Catalyst

Das¹,

Reddy²,

Sindhu³

et al. 2011

Helvetica Chimica Acta

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“…These conditions were then tested on 1-methyl-4-(phenylsulfonyl)-1H-furo [3,4-b]indol-3(4H)-one (17) to lead to the formation of 1-methyl-1H-furo [3,4-b]indol-3(4H)-one (18) 33 in excellent yield (entry 9). With this procedure, we avoid the opening of the lactone, 34 usually observed with the classical acidic or alkaline conditions, and only the sulfonyl group was removed in a quantitative yield.…”

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confidence: 99%

Desulfonylation of Indoles and 7-Azaindoles Using Sodium tert-Butoxide

Chaulet¹,

Croix²,

Basset³

et al. 2010

Synlett

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A mild method for the desulfonylation of N-indoles and N-azaindoles is described. Deprotection is carried out under basic conditions, using sodium tert-butoxide in dioxane. Several functionalized indoles and 7-azaindoles were efficiently deprotected by this method, which is mild enough to be used to deprotect compounds including functions that are known to be sensitive to acidic or basic conditions. Indoles and related structures are found in many active pharmaceutical molecules. [1][2][3][4][5] The NH group needs to be protected during synthetic pathways by a suitable group that can easily be removed at the end of the synthesis. The benzenesulfonyl group is one of the blocking groups commonly used to protect amines, because the resultant sulfonamides are more robust, confer crystallinity, and facilitate isolation. This group also modifies the polarity of the protected compound by withdrawing electrons. The methods for its deprotection are well known: dissolving metal reductions (Li or Na) in ammonia, HMPA, or alcohol; 6,7 sodium naphthalene 8 or anthracene, 9 Na-Hg, 10 Bu 3 SnH, 11,12 mischmetal with TiCl 4 , 13 SmI 2 , 14 Mg/ MeOH, 15,16 alkali metals in silica gel; 17 severe acidic conditions with H 2 SO 4 , 18 AcOH-HClO 4 , 19 48% HBr with PhOH and 30% HBr in AcOH, 20 KF on alumina under microwaves; 21 or basic conditions such as NaOH and KOH, 22,23 K 2 CO 3 in a acetonitrile, 24,25 Cs 2 CO 3 in THFMeOH, 26 n-Bu 4 NF in refluxing THF. [27][28][29] Most of these methods are effective in a number of cases, but are not compatible with other groups. We tried several of the methods described in the literature, but none of them gave satisfactory results.In a previous study, we were interested in the synthesis of compound 2. Treating 1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine-2-carboxylic acid (1) in the presence of K 2 CO 3 refluxing in a MeOH-H 2 O mixture 30 or using an aqueous solution of NaOH reflux in EtOH 31 led to degradation products. Moreover, observed desulfonylation instead of introduction of an amine into position 2 during attempted Buchwald-type coupling of 2-iodo-1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine 3 with aryl or alkylamines.This unexpected result has led us to develop a new and mild method to cleave the benzenesulfonyl moiety from protected indoles and related structures using sodium tertbutoxide. In order to determine the optimum stoichiometry, we carried out a series of experiments with 1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine-2-carboxylic acid (1).The amount of sodium tert-butoxide and the heating method (sealed tube or flask) were studied. The best results were obtained with the addition of 1.5 equivalents of sodium tert-butoxide and heating in a sealed tube at 80°C for three hours. Under these conditions, the derivative 2 was isolated with 92% yield.Under these new optimized conditions, 32 a variety of substituted indoles and azaindoles was subjected to N-desulfonylation with NaOt-Bu in dioxane. The results are shown in Table 1.The desulfonylation of unsubstituted N-sulfonyl-7-aza...

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Alkali Metals in Silica Gel (M-SG): A New Reagent for Desulfonation of Amines

Cited by 59 publications

References 48 publications

Hg cathode-free electrochemical detosylation of N,N-disubstituted p-toluenesulfonamides: mild, efficient, and selective removal of N-tosyl group

Hg cathode-free electrochemical detosylation of N,N-disubstituted p-toluenesulfonamides: mild, efficient, and selective removal of N-tosyl group

An Efficient Synthesis of [(Tosylamino)alkyl]naphthalenols by Nucleophilic Addition of Naphthalen‐2‐ol with N‐Tosyl Imines Using Boron Trifluoride Etherate as Catalyst

Desulfonylation of Indoles and 7-Azaindoles Using Sodium tert-Butoxide

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