Categories: C-N Bond Formation >
Synthesis of sulfonamides
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Recent Literature
A new, simple method for the conversion of alcohols to tosylamides is
presented.
M. C. Marcotullio, V. Campagna, S. Sternativo, F. Costantino, M. Curini,
Synthesis, 2006, 2760-2766.
Using 0.5 mol % [Ru(p-cymene)Cl2]2 with the bidentate
phosphines dppf or DPEphos as the catalyst, primary amines have been converted
into secondary amines, and secondary amines into tertiary amines. N-Heterocyclization
reactions of primary amines have been achieved, as well as alkylation reactions
of primary sulfonamides.
M. H. S. A. Hamid, C. L. Allen, G. W. Lamb, A. C. Maxwell, H. C. Maytum, A. J.
A. Watson, J. M. J. Williams, J. Am. Chem. Soc., 2009,
131, 1766-1774.
A catalytic amount of manganese dioxide and solvent-free conditions under air
enabled a practical and efficient N-alkylation method for a variety of
sulfonamides and amines using alcohols as green alkylating reagents.
X. Yu, C. Liu, L. Jiang, Q. Xu, Org. Lett., 2011,
13, 6184-6187.
Microwave heating enables a Borrowing Hydrogen strategy to form C-N bonds from
alcohols and amines, removes the need for solvent and reduces the reaction times,
while the results are comparable with those using thermal heating.
A. J. A. Watson, A. C. Maxwell, J. M. J. Williams, J. Org. Chem., 2011,
76, 2328-2331.
A convenient, general, and high yielding Pd-catalyzed cross-coupling of
methanesulfonamide with aryl bromides and chlorides eliminates concern over
genotoxic impurities that can arise when an aniline is reacted with
methanesulfonyl chloride. The application of this method to the synthesis of
dofetilide is also reported.
B. R. Rosen, J. C. Ruble, T. J. Beauchamp, A. Navarro, Org. Lett., 2011,
13, 2564-2567.
A biaryl phosphine ligand, t-BuXPhos and K3PO4 in
tert-amyl alcohol was found to be the optimal base-solvent combination
for a Pd-catalyzed sulfonamidation of aryl nonafluorobutanesulfonates. The
reaction conditions were tolerant of various functional groups. The only
identified limitation of this methodology is the inability of 2,6-disubstituted
aryl nonaflates to efficiently participate in the reaction.
S. Shekhar, T. B. Dunn, B. J. Kotecki, D. K. Montavon, S. C. Cullen, J. Org. Chem., 2011,
76, 4552-4553.
The arylation of N-H and O-H containing compounds at room temperature with
phenylboronic acids is promoted in the presence of cupric acetate and a tertiary
amine. Substrates include phenols, amines, anilines, amides, imides, ureas,
carbamates, and sulfonamides.
D. M. T. Chan, K. L. Monaco, R.-P. Wang, M. P. Winteres, Tetrahedron Lett.,
1998, 39, 2933-2936.
An efficient, mild and transition-metal-free N-arylation of amines,
sulfonamides, and carbamates and O-arylation of phenols and carboxylic acids has
been achieved by using various o-silylaryl triflates in the presence of CsF.
Z. Liu, R. C. Larock, J. Org. Chem., 2006,
71, 3198-3209.
A range of enol triflates can be coupled with amides, carbamates, and
sulfonamides using palladium catalysis. This method allows the synthesis of
enamides, which may not be readily available by other means.
D. J. Wallace, D. J. Klauber, C.-Y. Chen, R. P.
Volante, Org. Lett., 2003, 5, 4749-4752.
Nucleophilic addition of sulfonamides to 1-bromo-1-alkynes provided (Z)-N-(1-bromo-1-alken-2-yl)-p-toluenesulfonamides
in good yield and in a highly regio- and stereoselective manner. A subsequent
reaction in the presence of a palladium catalyst under Heck conditions afforded
substituted pyrroles in good yield.
M. Yamagishi, K. Nishigai, T. Hata, H. Urabe, Org. Lett., 2011,
13, 4873-4875.
Benzylic hydrocarbons are selectively converted to the corresponding
sulfonamides by the [Cu(CH3CN)4]PF6-catalyzed reaction with anhydrous
TolSO2NNaCl (chloramine-T). Under the same conditions, representative ethers
and olefins are
also amidated.
R. Bhuyan, K. M. Nicholas, Org. Lett., 2007,
9, 3957-3959.
A copper-catalyzed amidation of allylic and benzylic C-H is applicable to the
coupling of a diverse set of hydrocarbon species with aryl, heteroaryl, and
alkyl sulfonamides and is tolerant of a variety of functional groups.
G. Pelletier, D. A. Powell, Org. Lett., 2006,
8, 6031-6034.
A single Cu(II) catalyst couples a diverse range of nitrogen sources with
various alkynes and aldehydes without the addition of ligand or base.
Copper-catalyzed alkynylation involving p-toluenesulfonamide provides
high yields of N-Ts-protected propargylamines. The superior activity of
copper(II) triflate also allows this three-component alkynylation to incorporate
a ketone.
C. E. Meyet, C. J. Pierce, C. H. Larsen, Org. Lett., 2012,
14, 964-967.
The use of PhI=NTs/PhI=NNs as the nitrogen source in the presence of inexpensive iron(II) chloride + pyridine
as the in situ formed precatalyst enables amidation of aldehydes under mild conditions at room temperature or microwave assisted conditions.
The protocol is operationally straightforward and accomplished in good product yields and with complete chemoselectivity.
T. M. U. Ton, C. Tejo, S. Tania, J. W. W. Chang, P. W. H. Chan, J. Org. Chem., 2011,
76, 4894-4904.
A gold(I)-catalyzed decarboxylative amination of allylic N-tosylcarbamates
via base-induced aza-Claisen rearrangement in H2O allows the
synthesis of substituted N-tosyl allylic amines in good yield,
regioselectivity, and stereoselectivity. This transformation represents an
efficient and environmentally benign protocol for the synthesis of N-tosyl
allylic amines.
D. Xing, D. Yang, Org. Lett., 2010,
12, 1068-1071.
An economic and practical transformation from secondary alkyl-substituted
propargyl acetates to a variety of nucleophilic substitution products is
catalyzed by inexpensive InCl3. High yields and excellent
chemoselectivity were obtained. Five-, six-, and seven-membered propargyl
cycloethers were also successfully constructed.
M. Lin, L. Hao, X.-t. Liu, Q.-z. Chen, F. Wu, P. Yan, S.-x. Xu, X.-l. Chen, J.-j.
Wen, Z.-p. Zhan, Synlett, 2011,
665-670.
An efficient amidation reaction of saturated C-H bonds catalyzed by a unique
disilver(I) complex is reported. The reaction is stereospecific and practical
for the construction of amine-containing molecules.
Y. Cui, C. He, Angew. Chem. Int. Ed., 2004, 43, 4210-4212.
A highly efficient hydroamination of sulfonamides, carboxamides, and carbamates
with unactivated olefins is catalyzed by an inexpensive zirconium salt under
mild reaction conditions. The reactions gave good to excellent yields of the
Markovnikov products.
L. Yang, L.-W. Xu, W. Zhou, Y.-H. Gao, W. Sun, C.-G. Xia, Synlett, 2009,
1167-1171.
A simple addition of phenols, carboxylic acids, and protected amines to
olefins can be catalyzed by triflic acid. A low concentration of triflic
acid and control of the reaction temperature help to tolerate functional
groups, such as methoxyl substitution on aromatics.
Z. Li, J. Zhang, C. Brouwer, C.-G. Yang, N. W. Reich, C. He, Org. Lett.,
2006,
8, 4175-4178.
Addition of sulfonamides to alkenes and conjugated dienes can be carried out
using a low catalytic amount of (triphenyl phosphite)gold(I) chloride and silver
triflate under thermal or microwave conditions and at r.t. in the case of
dienes. Terminal alkenes undergo regioselective hydroamination at the internal
carbon atom and dienes at the less substituted double bond.
X. Giner, C. Nájera, Org. Lett.,
2008,
10, 2919-2922.
Ph3PAuOTf catalyzes efficient intra- and intermolecular
hydroamination of unactivated olefins with sulfonamides.
J. Zhang, C.-G. Yang, C. He, J. Am. Chem. Soc.,
2006,
128, 1798-1799.
A combined amino- and N-heterocyclic carbene (NHC)-catalyzed one-pot
reaction sequence using commercially available catalysts at low catalyst
loadings gives β-hydroxy and β-amino esters in high yield and excellent
enantiopurity. The generation of quaternary stereocenters and application in
gram-scale synthesis were also realized, with no requirements of inert or
anhydrous reaction conditions.
H. Jiang, B. Gschwend, Ł. Albrecht, K. A. Jřrgensen, Org. Lett., 2010,
12, 5052-5055.
The use of iodosobenzene (PhIO) as oxidant and p-toluenesulfonamide (TsNH2)
as aminating reagent in the presence of a catalytic amount of perchlorate zinc
hexahydrate enables a direct α-amination of β-dicarbonyl compounds. The reaction
proceeds quickly at rt to provide the corresponding α-N-tosylamido
β-dicarbonyl compounds very good yields.
J. Yu, S.-S. Liu, J. Cui, X.-S. Hou, C. Zhang, Org. Lett., 2012,
14, 832-835.
In copper-catalyzed direct N-alkynylation, the use of pure and anhydrous K3PO4
provides higher ynamide yields in comparison to samples contaminated with
hydrates (K3PO4 · 1.5 H2O and K3PO4
· 7 H2O). With high quality K3PO4, a
number of ynamides were synthesized in good yields. In addition, ynamides can
undergo regioselective hydroamination with carbamates.
K. Dooleweerd, H. Birkedal, T. Ruhland, T. Skrydstrup, J. Org. Chem., 2008,
73, 9447-9450.
A facile route to ynamides in high yields was achieved through an
iron-catalyzed C-N coupling reaction of amides with alkynyl bromides in the
presence of 20 mol % of N,N′-dimethylethane-1,2-diamine (DMEDA).
B. Yao, Z. Liang, T. Niu, Y. Zhang, J. Org. Chem., 2009,
74, 4630-4633.
A new procedure for aminobromination of olefins gives vicinal bromoamine derivatives in high yields using Cu, Mn, or V
catalysts with
p-toluenesulfonamide as nitrogen source and N-bromosuccinimide
(NBS) as bromine source. Excellent regio- and stereoselectivity is shown for different olefinic substrates as well as transition metal
catalysts.
V.
V. Thakur, S. K. Talluri, A. Sudalai, Org. Lett., 2003, 5,
861-864.
A convenient and efficient iron-catalyzed aminobromination of alkenes has been
developed using inexpensive FeCl2 as the catalyst,
amides/sulfonamides and NBS as the nitrogen and bromine sources, respectively,
under mild conditions.
Z. Wang, Y. Zhang, H. Fu, Y. Jiang, Y. Zhao, Synlett, 2008,
2667-2668.
A Rh(II)-catalyzed oxidative coupling of aldehydes and sulfonamides provides
N-sulfonylcarboxamides in one step. Various sulfonamides were found to react
with aromatic and aliphatic aldehydes to afford the desired products in very
good yields.
J. Chan, K. D. Baucom, J. A. Murry, J. Am. Chem. Soc., 2007,
129, 14106-14107.
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