sulfones in heterocyclic synthesis: advances in the ... · heating of...

Sulfones in heterocyclic synthesis: advancesin the chemistry of phenyl sulfonylacetophenone

Khaled M. Elattar1 • Ahmed Fekri1 • Nesma M. Bayoumy1,2 •

Ahmed A. Fadda1

Received: 19 October 2016 / Accepted: 10 January 2017 / Published online: 6 February 2017

� Springer Science+Business Media Dordrecht 2017

Abstract The present review provides a survey on the structural features, synthetic

methodologies, and reactions of phenyl sulfonylacetophenone, considered to be one

of the most important synthons in the field of synthetic organic chemistry. b-Ketosulfone is an active C–H acid which has been widely used as a nucleophile in

many organic transformations. It has been used for synthesis of five- and six-

membered ring systems containing one or two heteroatoms. In addition, it has been

used as a starting material for synthesis of fused heterocycles, cyclopropane,

cyclopentene, and cyclohexanone derivatives. b-Ketosulfone has been used for

synthesis of c- and d-ketosulfones, 1,4-diketones, amides, ethers, and substituted

benzene derivatives due to its high synthetic importance. It is a reactive interme-

diate in electrophilic reactions such as halogenation, alkylation, arylation,

heteroarylation, and coupling reactions, and is involved in other types of reaction

such as Diels–Alder condensation with aldehydes and desulfonylation. The mech-

anistic pathways of these reactions and their important synthetic applications are

discussed herein.

Keywords b-Ketosulfone � Synthesis � Reactions � Synthesis of heterocyclicsystems

& Khaled M. Elattar

[email protected]

1 Department of Chemistry, Faculty of Science, Mansoura University, El-Gomhoria Street,

Mansoura 35516, Egypt

2 Dental Biomaterials Department, Faculty of Oral and Dental Medicine, Delta University,

Gamasa, Egypt

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Res Chem Intermed (2017) 43:4227–4264

DOI 10.1007/s11164-017-2869-8

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AbbreviationsTHF Tetrahydrofuran

TMSCN Trimethylsilyl cyanide

DCM or

CH2Cl2

Dichloromethane

PTC Phase-transfer catalysis

THAB Tetrahexylammonium bromide

CAP N-Cyano-4-(dimethylamino)pyridinium bromide

DMF N,N-Dimethylformamide

DMF-DMA N,N-Dimethylformamide dimethylacetal

K2CO3 Potassium carbonate

TEA Triethylamine

LiTMP Lithium amide

Tf2O Trifluoromethylsulfonic anhydride

equiv. Equivalent

HEH Hantzsch ester (diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-

dicarboxylate)

DBU 1,8-Diazabicycloundec-7-ene

TMG 1,1,3,3-Tetramethylguanidine

MW Microwave

Zn Zinc

MeONa Sodium methoxide

DMSO Dimethyl sulfoxide

n-BuLi n-Butyllithium

CH3CN Acetonitrile

DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene

BNAH N-Benzyl-1,4-dihydronicotinamide

NaH Sodium hydride

MVK Methyl vinyl ketone

Bn Benzyl group

Ac Acetyl group

Introduction

b-Ketosulfones are considered to be reactive organic intermediates in many

synthetic pathways [1–4], being used as starting materials for Michael and

Knoevenagel reactions [5, 6] and in synthesis of acetylenes, allenes, chalcones

[7–12], vinyl sulfones [13], polyfunctionalized 4H-pyrans [14], and ketones

[15–18]. In addition, b-ketosulfones can be converted into optically active b-hydroxysulfones [19–21], halomethyl sulfones, and dihalomethyl sulfones [22].

Halomethyl sulfones and dihalomethyl sulfones are very good a-carbanionstabilizing substituents [23], precursors for synthesis of alkenes [24, 25], aziridines

[26], epoxides [27–31], b-hydroxysulfones [18–20], and have been used as vicariousnucleophilic substitution (VNS) adducts [32–34].

4228 K. M. Elattar et al.

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Haloalkyl sulfones are useful for preventing aquatic organisms from attaching to

fishing nets and ship hulls [35]. They also have other biological properties such as

herbicidal [36], bactericidal [37], antifungal [38], algicidal [39], and insecticidal

activity [40]. a-Halo b-ketosulfones and a,a-dihalo b-ketosulfones [22] can be

obtained by halogenation of b-ketosulfones with halogenating reagents such as

pyridinium perbromate, bromine, and sulfuryl chloride in chloroform/dichloro-

methane. However, a-chloro/bromo b-ketosulfones and chloro/bromomethyl sul-

fones do not undergo Finkelstein reactions [41, 42] to afford iodomethyl sulfones,

due to a strong retardation effect by the sulfone [43]. Further work on the

investigated compound promoted researchers to synthesize a,a-asymmetrical dihalo

b-ketosulfones [22, 44–47]. Recently, synthesis of b-ketosulfones, a-iodo b-ketosulfones, and iodomethyl sulfones was reported [48, 49]. In continuation of our

studies on the chemistry of sulfone and heterocyclic compounds [50–61], we report

herein the synthetic methods, reactions including mechanistic pathways, and

synthetic applications of phenyl sulfonylacetophenone.

Synthesis

From benzenesulfonyl chloride or its sodium salt

Phenyl sulfonylacetophenone (3) was obtained in 94% yield by reaction of sodium

benzenesulfinate (1) with phenyl acetylene (2) in water containing anhydrous ferric

chloride and dipotassium peroxodisulfate [62]. Irradiation of 1 with phenacyl

bromide (4a) in presence of aluminum oxide [63] or acylation of phenacyl chloride

(4b) using N-benzyl-N,N,N-triethylammonium chloride in acetonitrile [64] gave 3 in98 and 93% yield, respectively. Reaction of 4a with benzenesulfonyl chloride (5)[65] and reaction of 1 with acetophenone in presence of iodine in methanol

containing TEA gave 3 in 78 and 91% yield [66, 67]. Reaction of 5 with

trimethylsilyl phenyl acetylene gave 3 in 53% yield [68]. In addition, two-step

reaction of 1 with acetophenone O-acetyl oxime (8) in dimethyl sulfoxide

containing copper diacetate followed by treatment with silica gel in dichloro-

methane gave 3 in 93% yield [69]. Further reaction of 1 with styrene (9) in water

gave 3 in 93% yield (Scheme 1) [70].

From benzenesulfinic acid or benzenesulfonic acid

b-Ketosulfone 3 was prepared from reaction of benzenesulfinic acid with each of

phenyl acetylene (2) in 1,2-dichloroethane [71], styrene (9) in ethanol containing

anhydrous ferrous chloride [72], diethyl(1-phenylvinyl)phosphate (10), N-(1-

phenylvinyl)acetamide (11) in acetonitrile, (1-bromovinyl)benzene (12a) in THF

or (1-chlorovinyl)benzene (12b) in acetonitrile [73] in high yields. Via another

route, b-ketosulfone 3 was obtained in 20% yield by reaction of phenyl acetylene

(2) with benzenesulfonic acid in ethylene glycol and dimethyl ether containing

copper diacetate (Scheme 2) [74].

Sulfones in heterocyclic synthesis: advances in the… 4229

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From phenylthio acetophenone

On the other hand, b-ketosulfone 3 was prepared by heating 1-phenyl-2-

(phenylthio)ethanone (13) with AlCl3 (96%) [75] or heating with dihydrogen

peroxide in acetic acid (90%) [76]. Heating of 13 with magnesium monoperox-

yphthalate hexahydrate in DCM yielded 3 as the major product [77]. Reaction of

1-phenyl-2-(phenylthio)ethanol (14) with dipotassium peroxodisulfate in DMF gave

3 in 95% yield [78] (Scheme 3).

From 2-(phenylsulfonyl)acetonitrile

Heating of 2-(phenylsulfonyl)acetonitrile (16) with phenylboronic acid (17) in 1,4-

dioxane containing a few drops of HCl gave 3 in 97% yield [79] (Scheme 4).

Scheme 1 Synthesis of phenyl sulfonylacetophenone

Scheme 2 Synthesis of b-ketosulfone from sulfinic and sulfonic acids


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Miscellaneous methods

Heating 1-phenyl-2-(phenylsulfinyl)-2-(phenylsulfonyl)ethanone (18) in presence oftri-n-butyltin hydride and 2,20-azobisisobutyronitrile gave 3 in 88% yield [80].

Reaction of benzenesulfonohydrazide (19) with 9 in ethanol containing copper

diacetate gave 3 in 70% yield [81]. Also, b-ketosulfone 3 can be obtained using

other methods, i.e., heating of phenyl(1-phenyl-2-(phenylsulfonyl)vinyl)selane (20)in a mixture of trifluoroacetic acid/THF (84%) [82] and heating of 3-phenyl-2-

(phenylsulfonyl)acrylic acid (21) in 1,4-dioxane (20%) [83]. Treatment of

((phenylethynyl)sulfonyl)benzene (22) with methyl 3-oxobutanoate (23) in THF

gave 3 (32%) as the major product [84] (Scheme 5).

Scheme 3 Synthesis of b-ketosulfone from phenylthio acetophenone

Scheme 4 Synthesis of b-ketosulfone from 2-(phenylsulfonyl)acetonitrile

Scheme 5 Synthesis of b-ketosulfone 3


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In addition, b-ketosulfone 3 was obtained from reaction of 12a, b with diazonium

chloride in presence of sulfur dioxide and copper dichloride in acetic acid/acetone

(24, 15%, 10–20 �C) [85], and other methods have been reported [86–96].

Reactivity

Synthesis of five-membered ring containing one heteroatom

Synthesis of pyrrole, furan, and thiophene derivatives

Reaction of 3 with ammonium acetate in acetic acid gave pyrrole 25, while

acetylation of 3 with acetic anhydride produced furan 26. Thiophene derivative 27was synthesized in excellent isolated yield by reaction of 3 with Lawesson’s reagent

in THF (Scheme 6) [97].

Stirring of (alkoxycarbonylazo)-alkene 28 with b-ketosulfone 3 in THF at room

temperature afforded 1-alkoxycarbonylamino-3-sulfonylpyrrole 30 through initial

formation of the 1,4-adduct intermediate (29) (Scheme 7) [98].

On the other hand, heating b-ketosulfone 3 with aminocarbonylazoalkenes 31a–c in a mixture of benzene/AcOH catalyzed by piperidine led to intermediates 32,followed by cyclization after rearrangement in presence of copper chloride to give

1-ureido-3-sulfonylpyrroles 33a–c (Scheme 8) [99].

Under the optimized conditions (5 mol% of catalyst 35 in xylene at 0 �C), cyclicnitrones 37 were obtained from adducts 36. Nonselective reduction and desulfony-

lation reactions using Zn/NH4Cl provided cyclic nitrone 37a after 15 min at room

temperature. Compounds 37 were isolated in good yield as diastereoisomers starting

from 1:1 diastereomeric mixtures of 36 (Scheme 9) [100, 101].

Another route for synthesis of cyclic nitrones by one-pot reaction has also been

described. 1,4-Addition reaction of 34a and 3 was carried out under standard

Scheme 6 Synthesis of monocyclic systems


123

conditions, and activated Zn, THF, and saturated NH4Cl were added to the mixture

after 24 h. Nitrone 37a was isolated in good yield of 72%. Subsequent 1,3-addition

of TMSCN to nitrones 37 in presence of AlMe3 gave 38 in good yields (60–78%)

(Scheme 10) [100].

Condensation of b-ketosulfone 3 with aldehyde 39 in acetic acid/toluene

containing piperidine and magnesium sulfate for 6 h at 60 �C gave 1,5-diphenyl-2-

(phenylsulfonyl)pent-2-en-4-yn-1-one (40). 2-Benzoyl furan derivative 41 was

prepared in 79% yield by treatment of enyne derivative 11 with catalytic AuCl3 in

DCM at room temperature (Scheme 11). The mechanism for gold-catalyzed

oxidative cyclization was reported [102].

Knoevenagel condensation of b-ketosulfone 3 with benzaldehyde in a mixture of

acetic acid/benzene containing piperidine through stereoselective reaction gave a,b-unsaturated ketone 42 in 78% yield [103]. Reaction of a,b-unsaturated ketone 42with nitroalkane 43 in presence of alumina-supported potassium fluoride in

acetonitrile gave 2,3-dihydrofuran 44 (Scheme 12) [104].

Catalytic cyclizations of reactive cyclic enones 45a, b with b-ketosulfone 3involving acidic protons in presence of rubidium carbonate with catalytic amount of

quaternary ammonium salt as PTC at room temperature gave furan derivatives 46aand 46b in 81 and 62% yield, respectively (Scheme 13). After PTC screening,

THAB containing long hydrophobic chains gave the best results. The reaction in

Scheme 7 Synthesis of 1-alkoxycarbonylamino-3-sulfonylpyrrole

Scheme 8 Synthesis of 1-ureido-3-sulfonylpyrroles


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absence of PTC was much slower than the PTC-promoted reaction systems and

produced 46a in lower yield. This result reveals that the PTC seems to act as an

efficient catalyst for dramatic enhancement of reaction rate [105].

Thiophene-3-carbonitrile 47 (a type of five-membered ring containing one

heteroatom) was obtained in 68% yield by heating b-ketosulfone 3, sulfur, andmalononitrile in dry DMF containing triethylamine (Scheme 14) [106].

Scheme 9 Addition reaction of b-ketosulfone to nitroalkenes

Scheme 10 One-pot synthesis and TMSCN addition to nitrones


123

Synthesis of five-membered ring containing two heteroatoms

Synthesis of pyrazole derivatives

2-(5-Chlorobenzofuran-2-yl)-2-oxo-N0-phenylacetohydrazonoyl bromide (48) reactedwith b-ketosulfone 3 in ethanolic sodium ethoxide solution to yield (5-chloroben-

zofuran-2-yl)(1,5-diphenyl-4-(phenylsulfonyl)-1H-pyrazol-3-yl)methanone (50) in

74% yield [107]. The hydrazonoyl bromide 49 reacted with b-ketosulfone in

ethanolic sodium ethoxide at room temperature to give pyrazole derivative 51 in 82%

yield (Scheme 15) [108].

Scheme 11 Synthesis of furan derivative

Scheme 12 Synthesis of (phenylsulfonyl)-2,3-dihydrofuran

Scheme 13 Synthesis of tetrahydrobenzofuranone and cyclopenta[b]furanone derivatives

Scheme 14 Synthesis of substituted thiophene-3-carbonitrile


123

Synthesis of imidazolone

The unique ability of CAP to convert the sulfo nitrone 52 into the N-cyanoimida-

zolone 55 in high yield was reported. Alternative combinations of BrCN with other

bases exclusively afforded the a-bromonitrone 56 (Scheme 16) [109].

Synthesis of thiazole derivatives

Reaction of phenyl isothiocyanate with b-ketosulfone 3 in alkaline medium afforded

the nonisolable thiocarbamoyl intermediate 57. Upon reaction with bromo- and a-bromoketones, the latter underwent in situ heterocyclization to afford the

corresponding polyfunctionally substituted thiazoles 58a, b, 59, 60 and thiazo-

lidin-4-one 61 (Scheme 17) [110].

Synthesis of isoxazole derivatives

Heating of 3 with DMF-DMA in toluene for 15 h gave enamine derivative 62(77%). Reaction of 62 with hydroxylamine hydrochloride in methanol containing

sodium acetate afforded isoxazole 63. Treatment of isoxazole 63 with sodium

hydroxide in aqueous methanol at room temperature gave benzenesulfonylacetoni-

trile (65) in 34% yield. Ring-opening of 63 was carried out using a base to give

intermediate 64, which was further hydrolyzed to 65 (Scheme 18) [111].

Scheme 15 Reactions of b-ketosulfone with aryl hydrazones

Scheme 16 Synthesis of N-cyanoimidazolone


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b-Ketosulfone 3 reacted with pyrazole 66 in sodium ethoxide solution at room

temperature to give the isoxazole 67, which upon heating with hydrazine hydrate in

refluxing ethanol gave isoxazolyl-pyrazolo[3,4-d]pyridazinone 68 (Scheme 19)

[112].

Synthesis of six-membered ring containing one heteroatom

Synthesis of pyran derivatives

Stepwise reaction of b-ketosulfone 3 with paraformaldehyde at 100 �C in the

gluconic acid aqueous solution (GAAS)/meglumine system gave hydroxymethyl

Scheme 17 Synthesis of thiazole and thiazolidinone derivatives

Scheme 18 Route to phenylsulfonyl acetonitrile


123

derivative, followed by treatment with a-methylstyrenes 69 to produce 3,4-dihydro-

2H-pyran derivatives 70a–e in good yields (Scheme 20) [113].

Stereoselective epoxidation of 71 with meta-chloroperoxybenzoic acid (m-

CPBA) in refluxing DCM/DMF afforded 2H-pyran-3-ol derivatives 72 (80%) and

73 (10%) (Scheme 21) [114].

DABCO-catalyzed [3 ? 3] annulation of benzyl 3-(acetoxymethyl)penta-3,4-

dienoate (74) with b-ketosulfone 3 in DMF containing potassium carbonate yielded

the desired 4H-pyran derivative 75 (Scheme 22). For this transformation, a

stereogenic center is formed at C4 of 4H-pyran, allowing development of the

asymmetric version of annulation using chiral amine catalyst [115].

Hydropyrans 78a–c were prepared by treatment of b-ketosulfone 3 with

unsaturated aldehydes 76 in THF containing benzoic acid and catalytic amount of

silyl prolinol ether 77. The a-chiral center of sulfone can be eliminated by

intramolecular ketalization and subsequent dehydration of the alcohol groups in 79(Scheme 23) [116].

Scheme 19 Synthesis of isoxazolyl-pyrazolo[3,4-d]pyridazinone

Scheme 20 Three-component reaction of b-ketosulfone, paraformaldehyde, and styrenes


123

The reaction of Michael donor 3 with Michael acceptor 81 in ethanol containing

piperidine at room temperature gave the 2-amino-4H-pyran 82 in 27% yield

(Scheme 24) [14].

Synthesis of six-membered ring containing two heteroatoms

Synthesis of pyrimidines

Condensation of azidomethylthiourea 83 with sodium enolate of b-ketosulfone 3 in

acetonitrile containing sodium hydride yielded thiourea derivative 84 in 98% yield.

Cyclization of 84 by heating with p-toluenesulfonic acid in ethanol produced the

desired 3,4-dihydropyrimidine-2(1H)-thione 86 in 80% yield (Scheme 25) [117].

Scheme 21 Synthesis of 2H-pyran-3-ol derivatives

Scheme 22 Synthesis of 4H-pyran derivative via DABCO-catalyzed annulation

Scheme 23 One-pot synthesis of hydropyrans 78a–c


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Synthesis of fused heterocycles

Synthesis of furofuran and furopyrrole derivatives

Treatment of propargyl alcohol 87a with a-phenylsulfonyl chalcone 42a gave the

desired furofuran 88a. The reaction proceeded in presence of base (1.1 equiv) with

subsequent addition of Michael acceptor 42a with catalytic amount (5 mol%) of

palladium complex. The trifluorosulfonyl moiety is a better electron-withdrawing

group and a better leaving group than alkyl (or aryl) sulfones (Table 1) [118].

Synthesis of thienopyridine derivatives

Heating b-ketosulfone 3 with triethyl orthoformate in acetic anhydride furnished

1-benzoyl-1-phenylsulfonyl-2-ethoxyethene 89 in 65% yield. 5-Phenylsulfonyl

pyridinethione 91 was obtained in 75% yield from reaction of 89 with equimolar

amount of cyanothioacetamide 90 in refluxing acetonitrile solution. The

pyridinethione 91 reacted with chloroacetonitrile in ethanol containing K2CO3 to

afford thienopyridine derivative 92 (Scheme 26) [119].

Scheme 24 Reaction of b-ketosulfone with Michael acceptor

Scheme 25 Synthesis of 3,4-dihydropyrimidine-2(1H)-thione


123

Synthesis of pyrazolopyridines

One-pot cyclocondensation of b-ketosulfone 3, aldehyde, aminopyrazoles 93, and p-TsOH in boiling ethanol afforded adducts 94a–f (Scheme 27). Formation of 94a–f occurred in excellent yield and shorter reaction time under ultrasonic irradiation

compared with conventional conditions. The mechanistic pathway for formation of

1H-pyrazolo[3,4-b]pyridines 94a–f has been reported [120].

Synthesis of pyrazolopyrimidines and pyrimidobenzimidazoles

Treatment of 3 with aminopyrazoles and triethyl orthoformate in presence of

catalytic amount of piperidine afforded the corresponding pyrazolo[1,5-a]pyrim-

idines 96a–f. Similarly, treatment of sulfone 3 with 2-aminobenzimidazole (97)under the same reaction conditions afforded pyrimido[1,2-a]benzimidazole 98(Scheme 28) [121].

Table 1 Palladium-catalyzed cyclization of propargyl nucleophiles with a-sulfonyl-a,b-unsaturatedketonesa

Nu Acceptor Furan Yield (%) Nu Acceptor Furan Yield

(%)

57 87a 47

87a 52 87a 45

87a 58 42a 50

87a 42 42a 54

87a 60 42a 52

a Reactions conducted on 0.5 mM in refluxing THF with 87:42:(t-BuOK:PdCl2(PPh3)2) = 1.5:1:1.2:0.05


123

Reaction of 2-aminobenzimidazole (97) with various aldehydes and b-ketosul-fone 3 in DMF under microwave irradiation at room temperature afforded 2,4-

diarylpyrimido[1,2-a]benzimidazoles 100a–f (Scheme 29). The mechanism of

formation of 100a–f was reported [120].

Synthesis of triazolopyrimidines

Sulfone 3 reacted with 3-amino-1,2,4-triazole (101) to afford high yield of

[1,2,4]triazolo[1,5-a]pyrimidine 102 (Scheme 30) [121].

Synthesis of pyranochromenes

Knoevenagel condensation of b-ketosulfone 3 with aldehydes 103 and 106 in

toluene/acetonitrile mixture containing N,N0-bis(carboxymethyl)-ethylenediamine at

20 �C gave arylidene derivatives 104 and 107, respectively. Hetero–Diels–Alderreaction of 104 and 107 yielded the cis-annulated cycloadducts 105 and 108(Scheme 31) [122].

Scheme 26 Synthesis of (phenylsulfonyl)thieno[2,3-b]pyridine-2-carbonitrile

Ph

OS

Ph

OO

3

N NR

NH2

Ph

+

EtOHp-TsOH

MW or reflux

NN

NR

Ph Ar

Ph

94a-f93a, ba: R= H;

b: R= C6H5 a: R= H, Ar= C6H5 (MW 90%, reflux 71%)

b: R= H, Ar= 4-FC6H4 (MW 97%, reflux 76%)c: R= H, Ar= 4-ClC6H4 (MW 94%, reflux 75%)d: R= C6H5, Ar= C6H5 (MW 81%, reflux 60%)e: R= C6H5, Ar= 4-FC6H4 (MW 84%, reflux 63%)f: R= C6H5, Ar= 4-ClC6H4 (MW 84%, reflux 62%)

Ar-CHO

Scheme 27 Synthesis of pyrazolo[3,4-b]pyridines


123

Scheme 28 Route to fused pyrazolopyrimidines and pyrimidobenzimidazole

Ph

OS

Ph

OO

3

+DMF

MW or reflux97

a: Ar= C6H5 (MW 89%, reflux 69%)

b: Ar= 4-FC6H4 (MW 92%, reflux 75%)c: Ar= 4-ClC6H4 (MW 90%, reflux 72%)d: Ar= 4-BrC6H4 (MW 88%, reflux 70%)e: Ar= 2-ClC6H4 (MW 87%, reflux 69%)f: Ar= 4-CH3C6H4 (MW 88%, reflux 70%)

N

HN

NH2

99N

NNH2

ArSO2Ph

Ph

O

100a-fN

NN

Ph

Ar

-H2O-PhSO2H

Ar-CHO

Scheme 29 Synthesis of 2,4-diarylpyrimido[1,2-a]benzimidazoles

Scheme 30 Synthesis of triazolopyrimidines


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Synthesis of cycloalkanes

Synthesis of cyclopropanes

Vinylcyclopropane 110 was prepared in 72% yield by reaction of b-ketosulfone 3with allyl bromide (109) in THF containing LiTMP, followed by treatment with

Grubbs’ catalyst (Scheme 32) [123].

Reaction of b-ketosulfone 3, which has sulfone as an electron-withdrawing

group, with b-trifluoromethyl vinylsulfonium 111 in DMSO containing sodium

hydride at room temperature gave the desired product 112 (Scheme 33) [124].

Synthesis of cyclopentene, cyclopentone, and cyclopentane derivatives

The monoacetate 113 was coupled to the nucleophile generated from 3 via Pd-

catalyzed alkylation (Pd(PPh3)4/PPh3) in THF containing potassium carbonate at

40 �C to give compound 114 in 69% yield (Scheme 34) [125].

Reaction of b-ketosulfone 3 with (E)-but-2-enal (115) using a secondary amine/

N-heterocyclic carbene (NHC) dual catalytic system (amino catalyst 77 and NHC

precursor 117) produced cyclopentanone 116 in high yield with enantioselectivity

but modest diastereoselectivity of the cascade product (Scheme 35) [126].

Michael addition of dimethyl malonate to the enyne derivative 119 led to

intermediate 120 by proton transfer, followed by Cu-mediated cycloisomerization to

produce substituted methylenecyclopentanes 121. Compounds 124a–c were

obtained in 71–92% yield by slow addition (over 2 h) of enyne 119 to aryliodide

Scheme 31 Synthesis of pyrano[3,4-c]chromenes


123

(123a–c), dimethyl malonate (122), NaH (2.3 equiv.), (Pd(PPh3)4) as catalyst

(3 mol%), and CuI (6 mol%) (Scheme 36) [127].

Synthesis of cyclohexanones (Michael–aldol adducts)

Enantio- and diastereoselective domino Michael–aldol reaction of b-ketosulfone 3with a,b-unsaturated ketones 125 using a chiral imidazolidine catalyst (S)-126

Scheme 32 Synthesis of vinylcyclopropane

Scheme 33 Synthesis of substituted cyclopropane

Scheme 34 Synthesis of cyclopent-2-ene derivative via Pd(0) catalysis

Scheme 35 Synthesis of cyclopentanones


123

formed optically active cyclohexanones 130 having contiguous chiral centers. The

Michael–aldol adducts were formed as single diastereomers in up to 99% ee

(Scheme 37) [128].

Synthesis of c- and d-ketosulfones

Treatment of a mixture of 3 with methylsulfonyl chloride (1.5–2.0 equiv) in THF at

0 �C containing potassium hydroxide (8 equiv) for 10 min gave 132 in excellent

yield. 1-Phenyl-2-(((phenylsulfonyl)methyl)sulfonyl)ethanone (132) was prepared

by reaction of 131 with lithium diisopropylamide (LDA) (1 equiv) in THF at room

temperature (Scheme 38) [129].

Formation of 132 from sulfone 3 was achieved via formation of sulfene 134(Scheme 39), which was formed by reaction of sulfonyl halides with at least one a-hydrogen and tertiary bases [129].

Treatment of b-ketosulfone 3 with terminal alkynes gave the unsaturated d-ketosulfones 135 in good to excellent yield using rhenium catalysis. Insertion of the

alkynes into the nonstrained carbon–carbon single bond between the R- and b-positions of the b-ketosulfone proceeded, and (Z)-isomers were produced with high

regio- and stereoselectivity (Scheme 40) [130].

Synthesis of 1,4-diketones

Symmetrical 1,4-diketone 136 was synthesized from b-ketosulfone 3 by a visible-

light-induced C–S bond activation process. The reaction depended on the type of

Scheme 36 Synthesis and reactions of Michael acceptor


123

Scheme 37 Michael–aldol reaction of a,b-unsaturated ketones 125 with b-carbonyl compound catalyzedby (S)-126

Scheme 38 Synthesis of disulfonyl derivative

Scheme 39 Mechanism of formation of disulfonyl derivative


123

amine, solvent, and additives and proceeded under irradiation from a 3-W white

light-emitting diode (LED) (Scheme 41) [97].

Synthesis of amides

Treatment of b-ketosulfone (3) with electrophilic azide (triflyl azide) under standard

diazo transfer reaction conditions provided the desired diazo derivative 137 in 98%

yield [131–134]. Thermolysis of 137 in mesitylene afforded phenylsulfonyl phenyl

ketene (138), which reacted with aniline and benzyl amine to give amides 139a, b,respectively (Scheme 42) [135].

3-Oxo-N,3-diphenyl-2-(phenylsulfonyl)propanamide (141) was obtained in 74%

yield by reaction of b-ketosulfone 3 with 140 in THF (Scheme 43) [136].

Scheme 40 Reactions of b-ketosulfone with different alkynes

Scheme 41 Optimization of reaction conditions. Reagents: HEH, i-Pr2Net, n-Bu3N, TEA; Solvent:CH3CN, DMF, DMSO, MeOH; Additive: Cs2CO3, Na2CO3, K2CO3, DBU, 12–48 h, Yield 0–77%

Scheme 42 Synthesis of amides


123

Synthesis of ether derivative

Reaction of 3 with tosyl azide in ethanol containing TEA gave the diazo derivative

137. Thermolysis of diazo in methanol at 50–55 �C in presence of catalytic amounts

of copper powder and perchloric acid yielded 142 (Scheme 44) [137].

Enolization

Ru-substituted phenols catalyzed asymmetric hydrogenation of b-ketosulfone 3under 150 psi of H2 at 70 �C in EtOH with 1 mol% Ru(II) catalyst in presence of

iodine to give enantioenriched hydroxyl sulfone 143 with good catalytic efficiency

(Scheme 45). The structure of the catalyst is [RuCl(benzene)L]Cl, where L = li-

gand, and the yield (73–95.2%) depended on the type of ligand [138].

Halogenation

a-Halo b-ketosulfones 144 were synthesized using potassium halide and hydrogen

peroxide as chemoselective monohalogenation reagent. a,a-Symmetrical and

asymmetrical dihalo b-ketosulfones and a-halo, a-alkyl, and b-ketosulfones 145were prepared by reaction of 144 with bromine and sulfuryl dichloride in

dichloromethane containing TEA. Base-induced cleavage of a-halo b-ketosulfones,a,a-dihalo b-ketosulfones, and a-halo, a-alkyl b-ketosulfones afforded the corre-

sponding halomethyl sulfones, dihalomethyl sulfones, and haloalkyl sulfones 146(Scheme 46) [139].

Scheme 43 Synthesis of propanamide derivative

Scheme 44 Synthesis of 2-methoxy-1-phenyl-2-(phenylsulfonyl)ethanone (142)

Scheme 45 Preparation of (S)-1-phenyl-2-(phenylsulfonyl)ethanol (143)


123

Fluorination of b-ketosulfone 3 was carried out using SelectfluorTM in presence

of sodium carbonate in dry acetonitrile under inert atmosphere. Monofluoro b-ketosulfone 147 and difluoro b-ketosulfone 148 were obtained (Scheme 47) [140].

Diels–Alder reaction

Reaction of b-ketosulfone 3 with thionyl chloride led to a-oxo sulfine 151 providingthe ketone was sufficiently enolized. Reaction of trimethylsilyl enol ether 149 is a

more efficient and versatile method for synthesis of a-oxo sulfine 151. Sulfine 151 isentrapped by cycloaddition reaction with 2,3-dimethyl-l,3-butadiene to give 152(Scheme 48) [141].

Condensation with aldehydes

Knoevenagel condensation of b-ketosulfone 3 with aldehydes gave the unsaturated

sulfones 153a–d without solvent in presence of KF on alumina under microwave

irradiation (Scheme 49). The deprotonation is greatly facilitated by presence of an

adjacent electron-withdrawing group such as ketone [142].

Reaction of b-ketosulfone with aromatic aldehydes and ammonia should give the

3,4-dihydro-2H-1,3-oxazine derivatives 155, but the uncyclized 3-aryl-3-aryl-

methyleneamino-1-phenyl-2-phenylsulfonyl-propan-1-ones 154 were obtained.

Prop-2-en-3-one derivatives 156 were obtained as byproducts, while by refluxing

the reaction solutions, prop-2-enones 156 were obtained as sole products (Fig. 1)

[143].

Alkylation, arylation, and heteroarylation

Alkylation of b-ketosulfone 3 with ethyl iodide to give 157 in 95% yield was carried

out in an ultrasonic bath containing benzyl triethylammonium bromide and sodium

hydroxide in dichloromethane. The reaction could be done effectively under phase-

transfer conditions (Scheme 50) [144].

Scheme 46 Synthesis of a-halo b-ketosulfones and a,a-dihalo b-ketosulfones


123

b-Ketosulfone 3 was alkylated with allyl bromide (109) in benzene containing

DBU at room temperature to produce 1-phenyl-2-(phenylsulfonyl)pent-4-en-1-one

(158). Photoirradiation reaction of 158 using the BNAH-DMF/hm system gave

1-phenylpent-4-en-1-one (159) in 94% yield (Scheme 51) [17].

Reaction of 3 with allyl acetate (160) in presence of [{Pd-(C3H5)Cl}2] and a

variety of ligands gave the allyl product 161 in 83% yield (Scheme 52) [145].

Reaction of but-1-yn-1-ylbenzene (162) with 1.2 equivs. of 3 gave the

monoallylated product 3-methyl-1,5-diphenyl-2-(phenylsulfonyl)pent-4-en-1-one

Scheme 47 Fluorination of b-ketosulfone

Scheme 48 Diels–Alder reaction of sulfine with 2,3-dimethyl-l,3-butadiene

Scheme 49 Knoevenagel reaction of b-ketosulfone with aldehydes

Fig. 1 Multicomponent reaction of b-ketosulfone with aromatic aldehydes and ammonia


123

(163) in 95% yield (Scheme 53). Allylation of carbon nucleophiles with simple

alkyne was achieved using the palladium/acetic acid combined catalytic system

[146].

Irradiation reaction of allylbenzene (164) with sulfones 3a–c in acetic acid

catalyzed by copper diacetate and manganese diacetate gave moderate yields

(20–26%) of C-alkylated sulfones 165a–c (Scheme 54) [147].

Reaction of 3 with cinnamyl alcohols 166 with Pd(PPh3)4 and benzoic acid or

with 1-AdCOOH as additives under neat conditions in water gave 4-substituted-1-

phenyl-2-(phenylsulfonyl)but-3-en-1-ones 167a, b (Scheme 55) [148, 149].

Surprisingly, b-ketosulfone 3 reacted with formaldehyde and thiophenols at ratio

of 3/(HCHO)n/thiophenol = 1.0/1.0/1.2 in the GAAS/meglumine system to provide

thioethers 168a–l in high yields (Scheme 56) [113].

Using GAAS as medium, 169 reacted with many carbon-based nucleophiles,

such as 2-naphthol, N,N-dimethylaniline, pyrrole, 2-phenylindole, antipyrine, and

resorcinol, providing the corresponding Friedel–Crafts alkylation products 170a–f in good yields. GAAS might play the role of a mild acid catalyst, promoting

decomposition of 169 to produce the a-methylene-b-ketosulfone intermediate and

accelerating the Michael reaction of the intermediate and nucleophile (Scheme 57)

[113].

Monoallylation of 3 with 1.05 equiv. of allyl bromide (109) and K2CO3 in

acetone at reflux afforded 171 with a C-allylated group in 90% yield (Scheme 58)

[123].

Sodium enolate of ketone bearing the phenyl sulfonyl group at a-positiongenerated in situ by treating b-ketosulfone 3 with equivalent amount of NaH and

(trichloroethyl)urea 172 in acetonitrile (88%) or THF (76%) at room temperature

gave product 173 (Scheme 59) [150].

Treatment of 8-(but-3-en-2-yl)-9-isopropyl-6-methoxy-9H-purine (175) with b-ketosulfone 3 and sodium hydride (NaH) in dry THF containing Pd2dba3�CHCl3 ascatalyst at room temperature produced the desired E-alkene 176 (Scheme 60) [151].

Palladium-catalyzed reactions of aryl halide with b-ketosulfone 3 in 1,4-dioxane

catalyzed by Pd2dba3�CHCl3 (dba = dibenzylideneacetone), PPh3, and NaH as base

gave the monoarylation product 177 in 30% yield (Scheme 61) [152, 153].

2-Methylfuran (178) was used as a nucleophile in the GAAS/meglumine system.

The obtained product contained a b-ketosulfone fragment and a furan ring

(Scheme 62). The last step of the reaction mechanism could be Michael addition of

the formed methylene intermediate to 2-methylfuran [113].

Scheme 50 Alkylation of b-ketosulfone in basic medium


123

Scheme 51 Alkylation of b-ketosulfone followed by desulfonylation

Scheme 52 Enantioselective Pd-catalyzed allylic alkylations of acyclic ketones

Scheme 53 Alkylation of b-ketosulfone using catalytic palladium/acetic acid system

Scheme 54 Mn(OAc)3-mediated reactions in allylic series


123

Synthesis of substituted benzene derivatives (Michael–aldol adducts)

Michael reaction of 2-(phenylsulfonyl)acetophenone (3) with MVK in CH2Cl2containing TEA gave dione 180 in 88% yield. Further treatment of 180 with

NaOMe in MeOH gave the cyclized Aldol product 181 as a single diastereomer in

98% yield. The same product was also obtained in 80% yield from reaction of 3

Scheme 55 Pd-catalyzed allylic substitution

Scheme 56 Three-component reaction of b-ketosulfone, paraformaldehyde, and thiophenol or thiol

Scheme 57 Reactions of 169 with different nucleophiles in GAAS

Scheme 58 Allylation with allyl bromide


123

with MVK in sodium methoxide. The intramolecular Aldol reaction product 181 hasthe large substituent groups in equatorial position, thereby resulting in the most

stable diastereomer. Condensation of pyrrolidine with either 180 or 181 followed by

loss of water molecule and phenylsulfenic acid fragment provided the aromatic

substituted amine 184 (Scheme 63) [154].

As before, reaction of 3 with vinyl ketone in sodium methoxide produced the

Michael–aldol product 187 in 42% yield as a single diastereomer together with the

expected Michael adduct formed in 28% yield. Thermolysis of 187 with pyrrolidine

gave aryl amine 188 in 64% yield, whereas heating of 187 with thiophenol afforded

the aromatized sulfide 189 in 92% yield (Scheme 64) [154].

Michael–aldol reaction of 3 with 3-penten-2-one gave the expected cyclized

product 190 as a single diastereomer. Heating 190 with either pyrrolidine or

thiophenol produced the 1,3,5-trisubstituted aromatized amine 191 and the related

Scheme 59 Synthesis of 1-(1,1,1-trichloro-4-oxo-4-phenyl-3-(phenylsulfonyl)butan-2-yl)urea

Scheme 60 Alkylation of b-ketosulfone

Scheme 61 Synthesis of 1-phenyl-2-(phenylsulfonyl)-2-(4-(trifluoromethyl)phenyl)ethanone

Scheme 62 Three-component reaction of b-ketosulfone 3, paraformaldehyde, and 2-methylfuran


123

sulfide 192. Interestingly, the Michael addition product 193 formed as a 1:1 mixture

of diastereomers when 3 was reacted with 3-methylbut-3-en-2-one using NaOMe as

base. Heating 193 with pyrrolidine in presence of catalytic p-TsOH gave the 1,2,5-

trisubstituted aryl amine 194 in 57% yield. Similarly, thermolysis of 193 with

thiophenol afforded the related aromatic sulfide 195 in 90% yield (Scheme 65)

[154].

Scheme 63 Synthesis of substituted benzene and cyclohexanone derivatives

Scheme 64 Synthesis of substituted benzenes


123

Hydroxymethylation of b-ketosulfone

b-Ketosulfone 3, an active C–H acid which has been widely used as a nucleophile in

many organic transformations [140, 155], reacted with paraformaldehyde in various

solvents to give 196 and 169 (Scheme 66). The yields of the products depended on

the reaction time and solvent type [113].

Coupling reactions

Coupling of b-ketosulfone 3 with pyrazole diazonium chloride 197 in ethanol

containing sodium acetate gave hydrazone 198, which upon cyclization by loss of

water molecule yielded pyrazolo[5,1-c][1,2,4]triazine 199 (Scheme 67) [156].

Desulfonylation

One-pot desulfonylation of b-ketosulfone 3 was carried out using samarium and

mercury dichloride in THF to give oily acetophenone (200) in 65% yield with

disulfide formed as byproduct of reductive desulfonylation (Scheme 68) [157].

Formation of dimethyl acetal 201 by one-pot nucleophilic addition followed by

Julia elimination [158, 159] yielded olefin 202 in moderate yield with high

stereoselective control. On the other hand, reduction of the aldehyde 76d with

NaBH4 allowed efficient one-pot synthesis of the alcohol 204 (Scheme 69) [116].

Scheme 65 Synthesis of substituted benzene derivatives


123

Reduction of b-ketosulfone 3 with sake yeast provided the desired S-a-phenylsulfonylmethylbenzyl alcohol (S-3) (142) in 84% yield with 92% enan-

tiomeric excess. Desulfonylation of 142 with Raney nickel W-4 afforded 205without accompanying racemization (Scheme 70) [160].

Cinnamylation of b-ketosulfone

Mono-C-cinnamylation of b-ketosulfone 3 with K2CO3 in boiling acetone provided

206 in 89% yield. Stereoselective reduction of 206 with NaBH4 in methanol and

THF in ice bath gave 207 (87%) (Scheme 71) [114].

Miscellaneous reactions

Sc(OTf)3-Catalyzed transfer diazenylation of b-ketosulfone 3 with triazene 208 via

N–N bond cleavage was reported [161]. The transfer diazenylation reaction

Ph

OSO2Ph

3

+ (HCHO)nsolvent Ph

O

SO2 SO2PhO

Ph

Ph

OSO2Ph

OH196 169

+

Ph60 oC

SolventH2OglycerolPEG 400CH3CNClCH2CH2ClCH3NO2GAAS

Time (h)12121212121212

Yields (%) 196 (169)98 (0)10 (0)96 (0)40 (0)15 (0)5 (0)5 (0)

SolventGAAS/ meglumineH2O/ meglumineglycerol/ megluminePEG 400/ meglumineGAAS/ ethanolamineGAAS/ diethanolamineGAAS/ triethanolamineGAAS/ meglumine

Time (h)2424242412121212

Yields (%) 196 (169)5 (85)98 (0)90 (0)95 (0)40 (15)10 (72)<5 (<5)<5 (70)

Scheme 66 Reaction of b-ketosulfone with paraformaldehyde in different solvents

Scheme 67 Synthesis of pyrazolo[5,1-c][1,2,4]triazine

Scheme 68 Reductive desulfonylation of b-ketosulfone


123

proceeded using 1 equiv. TMSCl and 10 mol% Sc(OTf)3 in CH2Cl2 at 40 �C to give

azo compound 209 (Scheme 72).

Indeed, b-ketosulfone 3 was converted to the corresponding vinyl triflate 210 in

presence of LiOTf, amines, and triflic anhydride at room temperature. Interestingly,

excellent Z-stereoselectivity ([99:1) was observed (Scheme 73) [162].

Scheme 69 Enantioselective alkenylation by Julia olefination

Scheme 70 Reduction of b-ketosulfone followed by desulfonylation

Scheme 71 Cinnamylation of b-ketosulfone followed by reduction


123

Treatment of (1:1) b-ketosulfone 3 with 2-(methylthio)isoindoline-1,3-dione

(211) in DMSO containing potassium t-butoxide gave 2-(methylthio)-1-phenyl-2-

(phenylsulfonyl)ethanone (212) in 90% yield (Scheme 74) [163].

Conclusion

The phenyl sulfonylacetophenone motif is widely found in many synthetic organic

products and drug candidates with relevant biological activities. Furthermore,

phenyl sulfonylacetophenone (b-ketosulfone) is an attractive candidate to synthetic

chemists due to the ability of the motif to access a wide range of functional group

transformations, including synthesis of monocyclic, fused cyclic systems,

cycloalkanes, c- and d-ketosulfones, 1,4-diketones, amides, ethers, and substituted

benzene derivatives. Phenyl sulfonylacetophenone is synthesized, in general, from

benzenesulfonyl chloride or its sodium salt, benzenesulfinic or benzenesulfonic

acids, phenylthio acetophenone, 2-(phenylsulfonyl)acetonitrile, and other methods.

The synthetic importance of b-ketosulfone is discussed herein in detail, as well as

the reaction mechanisms.

Scheme 72 Sc(OTf)3-Catalyzed transfer diazenylation of b-ketosulfone

Scheme 73 Synthesis of vinyl triflate

Scheme 74 Reaction of b-ketosulfone with 2-(methylthio)isoindoline-1,3-dione


123

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