Categories: C-N Bond Formation >
Synthesis of sulfonamides
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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.
[(p-cymene)Ru(2,2'-bpyO)(H2O)] is a general and efficient
catalyst for the N-methylation of amines and sulfonamides with methanol
in the presence of a carbonate salt. The reaction tolerates a series of
sensitive substituents, such as nitro, ester, cyano, and vinyl groups.
P. Liu, N. T. Tung, X. Xu, J. Yang, F. Li, J. Org. Chem., 2021, 86,
2621-2631.
A water-soluble metal-ligand bifunctional dinuclear iridium complex catalyzes an
N-methylation of amines with methanol in aqueous solution. A range of desirable
products were obtained in high yields under environmentally benign conditions.
C. Meng, P. Liu, N. T. Tung, X. Han, F. Li, J. Org. Chem., 2020, 85,
5815-5824.
The combination of trimethyl phosphate (TMP) and Ca(OH)2 enables a
mild and efficient heteroatom methylation in DMF, water, or under neat
conditions, at 80 °C or at room temperature. A series of O-, N-, and
S-nucleophiles, including phenols, sulfonamides, N-heterocycles, such as
9H-carbazole, indole derivatives, and 1,8-naphthalimide, and aryl/alkyl
thiols, are suitable substrates.
Y. Tang, B. Yu, Synthesis, 2022, 54,
2373-2390.
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 borrowing hydrogen approach using a well-defined and bench-stable Mn(I) PNP
pincer precatalyst enables an efficient manganese-catalyzed N-alkylation
of sulfonamides with benzylic and simple primary aliphatic alcohols as
alkylating agents. A diverse range of aryl and alkyl sulfonamides undergoes
mono-N-alkylation in excellent yields.
B. G. Reed-Berendt, L. C. Morrill, J. Org. Chem., 2019, 84,
3715-3724.
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.
Halogen bonding induces an intermolecular Csp3-H amination and
even enables a hydrogen atom transfer relay strategy to access privileged
pyrrolidine structures directly from alkanes. Mechanistic studies support the
presence of multiple halogen bond interactions.
F. Wu, J. P. Ariyarathna, N. Kaur, N.-E. Alom, M. L. Kennell, O. H. Bassiouni,
W. Li,
Org. Lett., 2020, 22, 2135-2140.
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 base-catalyzed/promoted transition-metal-free direct alkylation of amines with
either aromatic or aliphatic alcohols provides the desired amines in good yields.
Q.-Q. Li, Z.-F. Xiao, C.-Z. Yao, H.-X. Zheng, Y.-B. Kang, Org. Lett.,
2015,
17, 5328-5331.
A catalyst-free
Petasis reaction of sulfonamides as amine components, glyoxylic acid, and aryl- or
alkenylboronic acids tolerates a
broad range of functional groups and provides a wide array of
α-amino acid derivatives.
A. M. Diehl, O. Ouadoudi, E. Andreadou, G. Manolikakes, Synthesis, 2018, 50,
3936-3946.
A palladium-catalyzed three-component synthesis of arylmethylsulfonamide
derivatives from sulfonamides, paraformaldehyde, and arylboronic acids is
operationally simple and provides a broad range of structurally interesting
sulfonamidomethyl compounds.
T. Beisel, G. Manolikakes,
Synthesis, 2016, 48, 379-386.
An intermolecular alkylation of sulfonamides with trichloroacetimidates occurs
in refluxing toluene without additives. Unsubstituted sulfonamides provide
better yields than more encumbered N-alkyl sulfonamides, whereas the
trichloroacetimidate alkylating agent must be a stable cation precursor.
D. R. Wallach, J. D. Chisholm, J. Org. Chem.,
2016, 81, 8035-8042.
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.
A mild and efficient method for the synthesis of N-arylsulfonamides in
the presence of CuCl as catalyst proceeds readily at room temperature in an open
flask using a variety of sulfonyl azides and boronic acids without any base,
ligand, or additive.
S.-Y. Moon, J. Nam, K. Rathwell, W.-S. Kim, Org. Lett., 2014,
16, 338-339.
An efficient method for the copper-catalyzed arylation of sulfonamides in water
under ligand-free conditions offers high yields, simple workup procedure, and
elimination of toxic materials.
M. Nasrollahzadeh, A. Ehsani, M. Maham, Synlett, 2014, 25,
505-508.
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.
A general and direct N-arylation of sulfonamides and NH-sulfoximines
by sodium arylsulfinates through a desulfitative pathway proceeded with
catalytic loadings of Cu(II) without any external ligands. This arylation
protocol offers high efficiency and good substituent tolerance.
Y. Jiang, Y. You, W. Dong, Z. Peng, Y. Zhang, D. An, J. Org. Chem.,
2017, 82, 5810-5818.
A C-N cross-coupling reaction of weakly nucleophilic N-arylsulfonamides
and aryl bromides provides N,N-diarylsulfonamides using Ni(cod)(DQ) as a
catalyst without additional ligands. The process is compatible with
electron-deficient and electron-rich aryl and heteroaryl bromides and can be
applied to late-state derivatizations.
T. You, J. Li, Org. Lett.,
2022, 24, 6642-6646.
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.
Iridium-catalyzed direct ortho C-H amidation of arenes works well with sulfonyl-
and aryl azides as the nitrogen source. The reaction proceeds efficiently with a
broad range of conventional directing groups with excellent functional group
compatibility under mild conditions via 5- as well as 6-membered iridacycle
intermediates.
D. Lee, Y. Kim, S. Chan, J. Org. Chem., 2013,
78, 11102-11109.
A
metal-free allylic amination of alkenes with simple sulfonamides and sulfamates allows the introduction of a wide
range of nitrogen functionality at the allylic position of alkenes with unique
regioselectivity and no allylic transposition in the presence of phosphine selenides or selenoureas
as catalysts.
W. P. Teh, D. C. Obenschain, B. M. Black, F. E. Michael, J. Am. Chem. Soc.,
2020, 142, 16716-16722.
A Facile Highly Regio- and Stereoselective Preparation of N-Tosyl
Allylic Amines from Allylic Alcohols and Tosyl Isocyanate via
Palladium(II)-Catalyzed Aminopalladation-β-Heteroatom Elimination
A. Lei, X. Lu,
Org. Lett., 2000, 2, 2357-2360.
An oxidative decarboxylation of β,γ-unsaturated carboxylic acids mediated by
PhI(OAc)2 gives the corresponding allylic acetates. In addition, a
decarboxylative C-N bond formation was achieved. Mechanistic studies suggest an
unique reactivity of hypervalent iodine reagents in this ionic oxidative
decarboxylation.
K. Kiyokawa, S. Yahata, T. Kojima, S. Minakata, Org. Lett.,
2014,
16, 4646-4649.
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.
The combination of Mg2+ and PF6- as
counteranion catalyzes a transition-metal-free dehydrative cross-coupling of
unactivated primary/secondary alcohols with amines/amides under environmentally
benign conditions. A wide range of allylic alcohols and amines/amides were
tolerated well in this efficient transformation.
H. Xing, M. Chen, D. Zhang, Z. Geng, P. Xie, T.-P. Loh, Org. Lett.,
2022, 24, 5657-5662.
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 palladium-catalyzed, enantioselective three-component reaction of
sulfonamides, aldehydes, and arylboronic acids generates a wide array of
α-arylamines with high yields and enantioselectivities. Notably, this process
tolerates air and moisture and provides an operationally simple approach
for the synthesis of chiral α-arylamines.
T. Beisel, G. Manolikakes, Org. Lett.,
2015,
17, 3162-3165.
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 robust transition-metal-free reaction of sulfonamides and (Z)-1,2-dichloroalkenes
or alkynyl chlorides enables the synthesis of internal and terminal ynamides.
The reaction tolerates various functional groups.
X. Zeng, Y. Tu, Z. Zhang, C. You, J. Wu, Z. Ye, J. Zhao, J. Org. Chem., 2019, 84,
4458-4466.
A crystalline ethynyl-1,2-benziodoxol-3(1H)-one (EBX)-acetonitrile
complex can be used for N-ethynylation of various sulfonamides under
mild conditions.
M. Yudasaka, D. Shimbo, T. Maruyama, N. Tada, A. Itoh, Org. Lett., 2019, 21,
1098-1102.
A robust one-step synthesis of ynamides from vinyl dichlorides and electron
deficient amides as cheap and easily available starting materials proceeds under
mild reaction conditions in open air In the absence of a transition-metal
catalyst. This strategy is not only suitable for the synthesis of both terminal
and internal ynamides but also amenable for large-scale preparation.
Y. Tu, X. Zeng, H. Wang, J. Zhao, Org. Lett.,
2018, 20, 280-283.
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.
An oxidative amination of allenes using a single hypervalent iodine reagent
proceeds very efficiently for monosubstituted allenes and leads to formation of
the corresponding propargylic amines, either as the internal or as the terminal
amine depending on the addition of triphenylphosphine oxide to the iodine(III)
reagent.
N. Purkait, S. Okumura, J. A. Souto, K. Muņiz, Org. Lett.,
2014,
16, 4750-4753.
Acid chlorides can be activated to transient acid iodide intermediates using a
simple iodide source. This indermediates undergo nucleophilic attack from a
variety of relatively weak nucleophiles - including Friedel-Crafts acylation of
N-methylpyrroles, N-acylation of sulfonamides, and acylation
reactions of hindered phenol derivatives.
R. J. Wakeham, J. E. Taylor, S. D. Bull, J. A. Morris, J. M. J. Williams, Org. Lett., 2013,
15, 702-705.
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 Co-catalyzed oxidant-free reaction of carboxylic acids with organic azides
in the presence of tert-butyl isocyanide enables an effective synthesis
of N-sulfonylcarboxamides in very good yields. The protocol offers short
times, low temperatures, and broad substrate scope.
Y. Fang, Z.-Y. Gu, S.-Y. Wang, J.-M. Yang, S.-J. Ji, J. Org. Chem., 2018, 83,
9364-9369.
Dibenzenesulfonimide is a nitrogen source of choice in terms of the yields and
the reaction time in a transition-metal-free intermolecular N-H insertion of
α-diazocarbonyl compounds. Primary mechanistic experiments suggest that a
pathway involves a sequence of protonation and nucleophilic substitution.
X. Luo, G. Chen, L. He, X. Huang, J. Org. Chem.,
2016,
81, 2943-2949.
N-Sulfonyl ketenimine formation followed by a probable 1,3-OAc migration
([3,3]-sigmatropic rearrangement) enables a synthesis of trans-α,β-unsaturated
N-tosylamides from readily accessible propargyl acetates and sulfonyl
azides in the presence of CuI as catalyst. The reaction is very general and
affords products at ambient temperature with excellent diastereoselectivity in
good yields.
Y. K. Kumar, G. R. Kumar, M. S. Reddy, J. Org. Chem., 2014,
79, 823-828.
A combination of N-bromoimide and DBU enables allylic amination reactions
of alkenes, in which both internal and external nitrogen nucleophiles can be
installed directly. Dual activation of NBS or NBP by DBU leads to more
electrophilic bromine and more nucleophilic nitrogen atoms simultaneously. This
protocol provides a complementary access to allylic amination under mild
conditions.
Y. Wei, F. Liang, X. Zhang, Org. Lett., 2013,
15, 5186-5189.
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.
Orangoselenium catalysis enables an efficient route to 3-amino allylic alcohols
in excellent regio- and stereoselectivity in the presence of a base. In the
absence of bases α,β-unsaturated aldehydes were formed in excellent yield. The
hydroxy group is crucial for the direct amination.
Z. Deng, J. Wei, L. Liao, H. Huang, X. Zhao, Org. Lett.,
2015,
17, 1834-1837.
A reaction between terminal alkynes and sulfonamides under ambient
air using PIDA (diacetoxy iodobenzene) provides α-sulfonylamino ketones. This
metal-free reaction offers a broad substrate scope, excellent regioselectivity,
easily accessible reactants, and mild reaction conditions and is operationally
simple.
S. Mahato, S. Santra, G. V. Zyryanov, A. Majee, J. Org. Chem., 2019, 84,
3176-3183.
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 general Pd-catalyzed, enantioselective three-component synthesis using readily
available sulfonamides, glyoxylic acid derivatives, and boronic acids provides a
broad range of α-arylglycines in high yields and excellent levels of
enantioselectivity. Incorporation of Pbf-amides gives a racemization-free access
to N-unprotected α-arylglycines.
T. Beisel, A. M. Diehl, G. Manolikakes, Org. Lett.,
2016, 18, 4032-4035.
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. Jørgensen, 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 direct metal-free amination of arylalkynes with the hypervalent iodine
reagent PhI(OAc)NTs2 provides rapid access to ynamides in an
unprecedented intermolecular C-H to C-N bond conversion reaction. A related
transformation between alkylated alkynes and the iodine(III) reagent gives
cyclopentene amides.
J. A. Souto, P. Becker, A. Iglesias, K. Muņiz, J. Am. Chem. Soc., 2012,
134, 15505-15511.
An efficient intermolecular trans-selective β-hydroamidation of
ynamides provides (Z)-ethene-1,2-diamide derivatives with excellent
regio- and stereo-selectivities for a wide range of substrates. The reaction
proceeds under basic conditions in the absence of a transition-metal catalyst.
Z. Peng, Z. Zhang, Y. Tu, X. Zeng, J. Zhao, Org. Lett.,
2018, 20, 5688-5691.
Rhodium(II) azavinyl carbenes, which are conveniently generated from
1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal
1,3-insertion into N-H and O-H bonds of primary and secondary amides, various
alcohols, and carboxylic acids to afford a wide range of vicinally
bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity.
S. Chuprakov, B. T. Worrell, N. Selander, R. K. Sit, V. V. Fokin, J. Am. Chem. Soc., 2014,
136, 195-202.
A catalyst- and metal-free visible-light-mediated protocol enables the
iodoamination of miscellaneous olefins in high yields under environmentally
benign reaction conditions using DMC as green and biodegradable solvent.
Furthermore, the protocol allows for late-stage functionalization of bioactive
molecules and can be scaled to gram quantities of product.
S. Engl, O. Reiser, Org. Lett., 2021, 23,
5581-5586.
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.
In an efficient, catalyst-free, and metal-free bromoamidation of unactivated
olefins, 4-(trifluoromethyl)benzenesulfonamide and N-bromosuccinimide
were used as the nitrogen and halogen sources, respectively. The methodology is
applicable to both cyclic and aliphatic olefins.
W. Z. Yu, F. Chen, Y. A. Cheng, Y.-Y. Yeung, J. Org. Chem.,
2015,
80, 2815-2821.
An aminohalogenation of cinnamic esters with N,N-dichloro-p-toluenesulfonamide
provides vicinal chloroamine derivatives in very good yields. The reaction was
performed in MeCN using ZnCl2 or Cu(OTf)2 as catalyst. The
stereochemistry was unambiguously determined by transforming one of the products
to a known sample.
G. Li, H.-X. Wei, S. H. Kim, M. Neighbors,
Org. Lett., 1999, 1, 395-397.
The direct oxidative N-acylation reaction of primary amides with aryl/α,β-unsaturated
aldehydes was achieved in the presence of an azolium salt and an inorganic base
using 3,3′,5,5′-tetra-tert-butyldiphenoquinone as the oxidant. The
reaction provides an efficient approach for the synthesis of N-sulfonylcarboxamides,
N-sulfinylcarboxamides, and dicarboxyimides in good yield.
C. Zheng, Y. Liu, C. Ma, J. Org. Chem.,
2017, 82, 6940-6945.
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.
In a highly regioselective, direct visible-light-mediated aminofluorination of
styrenes, a shelf-stable N-Ts-protected 1-aminopyridine salt serves as
the nitrogen-radical precursor, and the commercially available hydrogen
fluoride-pyridine was used as the nucleophilic fluoride source.
J.-N. Mo, W.-L. Yu, J.-Q. Chen, X.-Q. Hu, P.-F. Xu, Org. Lett.,
2018, 20, 4471-4474.
In a copper-catalyzed intermolecular aminoalkynylation of alkenes, N-fluoro-N-alkylsulfonamides
(NFASs) are used as nitrogen-centered radical precursors and
alkynyltrimethoxysilanes as alkynylating reagents. This radical relay process
presents an efficient and straightforward approach to various highly
enantioenriched 2-alkynyl-2-arylethylamines in good yields.
Z. Hu, L. Fu, P. Chen, W. Cao, G. Liu, Org. Lett., 2021, 23,
107-112.
Related:
A series of vinyl sulfonamides was synthesized using the Horner reaction of
aldehydes and diphenylphosphorylmethanesulfonamide. The sulfonamide reagent was
easily prepared and can be stored indefinitely.
D. C. Reuter, J. E. McIntosh, A. C. Guinn, A. M. Madera, Synthesis,
2003, 2321-2324.
A Zn/CuI-mediated coupling of alkyl halides with
vinyl sulfones, vinyl sulfonates, and vinyl sulfonamides is described. Formamide is a superior solvent for obtaining
high yields.
M. M. Zhao, C. Qu, J. E. Lynch, J. Org. Chem., 2005,
70, 6944-6947.
Ynamides are moisture-sensitive and prone to hydration especially under
acidic and heating conditions. An environmentally benign, robust Sonogashira
coupling
enables the synthesis of sulfonamide-based ynamides and arylynamines in water, using a readily available quaternary
ammonium salt as the surfactant.
L. Zhao, H. Yang, R. Li, Y. Tao, X.-F. Guo, E. A. Anderson, A. Whiting, N.
Wu, J. Org. Chem., 2021, 86,
1938-1947.
A copper-catalyzed coupling of Grignard or organozinc
nucleophiles with chloroynamides, formed in situ from 1,2-dichloroenamides,
provides a broad range of ynamides. The reaction is readily scaled and overcomes
typical limitations in ynamide synthesis such as the use of ureas, carbamates,
and bulky or aromatic amide derivatives.
S. J. Mansfield, R. C. Smith, J. R. J. Yong, O. L. Garry, E. A. Anderson,
Org. Lett., 2019, 21, 2918-2922.