2,3-Dihydro-3-oxo-2-phenyliodonium-benzo[b]thiolenide-1,1-dioxide: Synthesis, decomposition and Cu-catalyzed thermal reactions

“…2-Isopropenyl-2-methyl-3,5,6,7-tetrahydro-2H-benzofuran-4one ( 13 C NMR (75 MHz, CDCl 3 ): d = 195.7, 176.1, 146.6, 112.5, 110.1, 93.4, 37.4, 36.4, 26.2, 24.0, 21.7, 18.5 198.4, 173.91, 139.1, 126.4, 112.9, 72.0, 36.9, 30.9, 28.2, 27.9, 20.3 -2-methyl-6-phenyl-3,5,6,7-tetrahydro-2H-benzofuran-4-one (50) and 3,4-Dimethyl-8-phenyl-5,6,8,9-tetrahydro-2H-benzo[b]oxepin-6-one (51) Reaction of 3 (390 mg, 1 mmol) with 2,3-dimethyl-1,3-butadiene (2 mL) using Rh 2 (OPiv) 4 (3 mg, 0.005 mmol) afforded 50 (121 mg, 45%) as a mixture of diastereomers and 51 (129 mg, 48%). -2-methyl-6-phenyl-3,5,6,7-tetrahydro-2H-benzofuran-4-one (50) IR (neat): 3090,3030,2976,2936,1636,1453,1402,1373,1346,1254,1233,1123,1026,905 3,4-Dimethyl-8-phenyl-5,6,8,9-tetrahydro-2H-benzo[b]oxepin-6-one (51) IR (neat): 3028,2911,1649,1603,1453,1393,1354,1302,1262,1128,1105,1042,970,949 Isopropenyl-2,6,6-trimethyl-3,5,6,7-tetrahydro-2H-benzofuran-4-one (52) and 3,4,8,8-Tetramethyl-5,7,8,9-tetrahydro-2Hbenzo[b]oxepin-6-one (53) Reaction of 4 (342 mg, 1 mmol) with 2,3-dimethyl-1,3-butadiene (2 mL) using Rh 2 (OPiv) 4 (3 mg, 0.005 mmol) afforded 52 (93 mg, 42%) and 53 (117 mg, 53%).…”

Section: Reactions With 13-butadienes; General Proceduresmentioning

confidence: 99%

“…All the above mentioned reactions could be explained by a carbene or carbenoid intermediate, as proposed by another group. 13 The iodonium ylide 4 first gives a carbene 22 (or carbenoid) by displacement of iodobenzene by Rh 2 (OPiv) 4 , which reacts with conjugated esters. The formation of 7 may involve the 1,3-dipolar cycloaddition of the carbene to the electron deficient olefin (path a) or initial cyclopropanation followed by ring cleavage to give zwitterions 24 (path b).…”

mentioning

confidence: 99%

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Rhodium(II)-Catalyzed Reaction of Iodonium Ylides with Conjugated Compounds: Efficient Synthesis of Dihydrofurans, Oxazoles, and Dihydrooxepines

Lee¹,

Yoon²,

Seo³

et al. 2004

Synthesis

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R h o d i u m ( I I ) -C a t a l y z e d R e a c t i o n o f I o d o n i u m Y l i d e s w i t h C o n j u g a t e d C o m p o u n d sAbstract: The rhodium(II)-catalyzed reaction of iodonium ylides with a variety of conjugated compounds has been examined. With a,b-unsaturated esters and a,b-unsaturated ketones, dihydrofurans were produced in moderate yields. Reactions with acrylonitriles yield oxazoles and dihydrofurans in moderate yields, whereas reactions with 1,3-butadienes result in dihydrofurans and dihydrooxepines in good yields, respectively. The mechanistic pathway for the formation of these products has been described in terms of a cyclopropane intermediate or a 1,3-dipolar cycloaddition mechanism.Iodonium ylides are attractive and important reagents in organic synthesis. 1 Iodonium ylides are widely used as equivalents of the corresponding diazo compounds. Intermolecular and intramolecular photochemical and metalmediated reactions of iodonium ylides with a number of electron rich olefins have been widely studied by several groups. 2 The reactions include C-H and N-H insertions, 3 Wolff-rearrangement, 4 cyclopropanation, 5 and cycloaddition. 6 Although these reactions have aroused great interest in reactions for the synthesis of 5-membered cycles or heterocycles, 7 there is little information available on the rhodium(II)-catalyzed reactions of iodonium ylides to electron deficient olefins. Recently, we have reported on the rhodium(II)-catalyzed reaction of iodonium ylides with halides and heterocyclic compounds. 8 While continuing our work based on iodonium ylides, we have expanded this work to conjugated compounds. The reactions seem ideal for the synthesis of dihydrofuran, oxazole, and dihydrooxepine derivatives that have been widely found in nature 9 and have shown a number of biological activities. 10 We report here our results on the rhodium(II)-catalyzed reaction of iodonium ylides with a,b-unsaturated esters, a,b-unsaturated ketones, acrylonitriles, and 1,3-butadienes to give 5-and 7-membered heterocycles such as dihydrofurans, oxazoles, and dihydrooxepines.Iodonium ylides 1-6 were prepared by the reaction of the corresponding 1,3-dicarbonyl compounds with iodobenzene diacetate according to Koser's method (Figure 1). 11 In order to check the reactivity of conjugated compounds, reactions with a,b-unsaturated esters were first examined utilizing several metal catalysts. When iodonium ylide 4 was treated with ethyl acrylate as a solvent and a reactant at 60 °C for 24 hours in the presence of 1 mol% of copper(II) acetate, no products were produced. Both palladium(II) acetate and Rh 2 (OCOCF 3 ) 4 catalysts afforded a small fraction of the product in 10% and 15% yields, respectively. Rh 2 (OAc) 4 and Rh 2 (OPiv) 4 catalysts provided product 7 in 42% and 60% yields, respectively. However, we found that Rh 2 (OPiv) 4 was a much superior reagent for this cycloaddition than Rh 2 (OAc) 4 with the advantage of more mild reaction conditions and a higher yield (Table 1). This reaction was also produced in so...

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“…Ôá éωäο υëßäéá τωí â-äéêáñâοíυëéêþí åíþóåωí áποτåëούí τυπéêÞ πηãÞ 1,3-äéπüëωí, áíτéäñούí ìå äéÜöοñåò áêüñåóτåò åíþóåéò êáé äßíουí πñοúüíτá êυêëοπñοóθÞêηò ìå óύã÷ñοíη áπüóπáóη éωäοâåíaeοëßου. [5][6][7]21,33,62,[77][78][79][80][81] Åπßóηò, áíτéäñούí ìå äéÜöοñá äéποëáñüöéëá, üπωò äéθåéÜíθñáêá, íéτñßëéá, θåéοâåíaeοöáéíüíåò êáé êåτÝíåò êáé οäηãούí óå åτåñοêυêëéêÜ πñοúüíτá. Ïé áíτéäñÜóåéò êυêëοπñοóθÞêηò τωí éωäο υëéäßωí áπáéτούí τη ÷ñÞóη êáτáëυτéêÞò ποóüτητáò áëÜτωí ÷áëêού Þ ñοäßου, áí êáé ο áêñéâÞò ìη÷áíéóìüò τηò äéáäéêáóßáò äåí åßíáé áêüìη îåêÜθáñοò.…”

Section: áíτιδñüóåιò êυêëïπñïóθþêηòunclassified

Αντιδράσεις Των Ιωδο Υλιδίων Β-Δισουλφονών Και Β-Δικετονών

Νυχάς¹

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ÐÅÑÉÅ×ÏÌÅÍÁ ÅÉÓÁÃÙÃÇ 1. Õëßäéá του Ιωäßου 1.1 ΙóτοñéêÞ áíáäñοìÞ 1.2 ÃåíéêÞ äοìÞ τωí υëéäßωí του éωäßου 1.3 ΠáñáóêåυÞ τωí éωäο υëéäßωí êáé áποóύíθåóη 1.4 ÁíτéäñÜóåéò τωí éωäο υëéäßωí 1.4.1 ÁíτéäñÜóåéò ìå ηëåêτñοíéüöéëá áíτéäñáóτÞñéá 1.4.2 ÁíτéäñÜóåéò ÊυêëοπñοóθÞêηò 1.4.3 ÁíτéäñÜóåéò Ôñáíóυëéäßωóηò 1.4.4 Áaeéñéäéíßωóη êáé áìßíωóη 1.5 Ιωäο υëßäéá öáéíοëþí Þ 1,4-äßποëá 1.6 Ιωäο υëßäéá τωí â-äéóουëöοíþí ÁÐÏÔÅËÅÓÌÁÔÁ-ÓÕAEÇÔÇÓÇ 2. Ιωäο υëßäéá â-äéóουëöοíþí 2.1 ΠáñáóêåυÞ éωäο υëéäßωí â-äéóουëöοíþí êáé áποóύíθåóη 2.2 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο êáé éωäοáëêÜíéá 2.3 ×áëêüíåò. Óύíθåóη êáé åöáñìοãÝò 2.4 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå ÷áëêüíåò 3. Ιωäο υëßäéá â-äéêáñâοíυëéêþí åíþóåωí 3.1 Óύíθåóη τωí â-äéêáñâοíυëéêþí éωäο υëéäßωí êáé áποóύíθåóη 3.2 ÁíτéäñÜóåéò êυêëοπñοóθÞêηò éωäο υëéäßωí 3.2.1 ÁíτéäñÜóåéò ìå áëêÝíéá 3.2.2 ÁíτéäñÜóåéò ìå áëêßíéá 3.2.3 ÁíτéäñÜóåéò ìå äéÝíéá 3.2.4 ÁíτéäñÜóåéò ìå öουñÜíéá 3.2.5 ÁíτéäñÜóåéò ìå θåéοêáñâοíυëéêÝò åíþóåéò 3.2.6 ÁíτéäñÜóåéò ìå äéöáéíυëο êåτÝíη ÐÅÉÑÁÌÁÔÉÊÏ ÌÅÑÏÓ 4.1 ÓυóêåυÝò-¼ñãáíá 4.2 Óύíθåóη τωí â-äéóουëöοíþí êáé τωí áíτßóτοé÷ωí éωäο υëéäßωí 4.3 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο ii 4.4 ÁíτéäñÜóåéò éωäο υëéäßωí τωí â-äéóουëöοíþí µå áëêυëοúωäßäéá 4.5 Óύíθåóη ×áëêοíþí 4.6 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå ÷áëêüíåò 4.7 Óύíθåóη τωí â-äéêáñâοíυëéêþí éωäο υëéäßωí êáé áποóύíθåóη 4.8 ÁíτéäñÜóåéò ìå áëêÝíéá 4.9 ÁíτéäñÜóåéò ìå áëêßíéá 4.10 ÁíτéäñÜóåéò ìå äéÝíéá 4.11 ÁíτéäñÜóåéò ìå öουñÜíéá 4.12 ÁíτéäñÜóåéò ìå θåéοêáñâοíυëéêÝò åíþóåéò 4.13 ÁíτéäñÜóåéò ìå äéöáéíυëο êåτÝíη ÐÅÑÉËÇΨÇ 5. Πåñßëηøη ÂÉÂËÉÏÃÑÁÖÉÁ 6. Âéâëéοãñáößá 141 iii Ðñüëïãïò Ôá υëßäéá του éωäßου áποτåëούí ìéá τÜîη åíþóåωí του υπåñóθåíούò éωäßου, οé οποßåò âñßóêουí ποéêßëåò åöáñìοãÝò óτηí οñãáíéêÞ óύíθåóη. Óêοπüò τηò πáñούóáò åñãáóßáò Þτáí η ìåëÝτη τωí áíτéäñÜóåωí τωí éωäο υëéäßωí τωí â-äéóουëöοíþí, êáθþò êáé τωí êυêëéêþí â-äéêáñâοíυëéêþí éωäο υëéäßωí. ÁíáëυτéêÜ åîåτÜóτηêáí οé áíτéäñÜóåéò τωí éωäο υëéäßωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο, πáñουóßá Þ ìη, áëêυëο éωäéäßωí, êáθþò êáé οé áíτéäñÜóåéò τουò ìå ìéá ποéêéëßá ÷áëêοíþí. ÅîåτÜóτηêáí, åπßóηò, οé áíτéäñÜóåéò τωí éωäο υëéäßωí τηò 1,3êυêëοåîáíοäéüíηò êáé 1,3-êυêëοπåíτáíοäéüíηò ìå πëηθþñá äéποëáñüöéëωí óå äéÜöοñåò óυíθÞêåò áíτßäñáóηò, οé οποßåò Ýäωóáí τá πñοéüíτá êυêëοπñοóθÞêηò ìå ìÝτñéåò åþò êáëÝò áποäüóåéò. Ïé áíτéäñÜóåéò τωí éωäο υëéäßωí τωí â-äéóουëöοíþí ìå áëêυëο éωäßäéá οäÞãηóáí óτá áíτßóτοé÷á áëêυëáëοãοíßäéá êáé óå áëêυëο υποêáτåóτηìÝíåò äéóουëöüíåò. Ïé áíτéäñÜóåéò τωí éωäο υëéäßωí τωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο οäÞãηóáí óτá éíäáíéêÜ πáñÜãωãá, åíþ η áíτßäñáóη ìå íοñâοíυëÝíéο πáñουóßá éωäοìåθáíßου οäÞãηóå óτο πñοúüí ηëåêτñοíéüöéëηò πñοóθÞêηò óτοí äéπëο äåóìü του íοñâοíυëåíßου. Ïé áíτéäñÜóåéò τωí äéò(áñυëοóουëöοíυëο)éωäο υëéäßωí ìå ÷áëêüíåò οäÞãηóáí óå éíäáíéêÜ πáñÜãωãá, óå πñοéüíτá äéÜóπáóηò, πáñåìâοëÞò óτοí οëåöéíéêü C-H äåóìü êáé óå öëáâáíüíåò. Ïé áíτéäñÜóåéò τωí â-äéêáñâοíυëéêþí éωäο υëéäßωí ìå áëêÝíéá, áëêßíéá, äéÝíéá, öουñÜíéá, θåéού÷á äéποëáñüöéëá êáé êåτÝíåò, οäÞãηóáí óτá áíτßóτοé÷á πñοúüíτá êυêëοπñοóθÞêηò, που...

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2,3-Dihydro-3-oxo-2-phenyliodonium-benzo[b]thiolenide-1,1-dioxide: Synthesis, decomposition and Cu-catalyzed thermal reactions

Cited by 18 publications

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Synthesis and chemical properties of cyclic β-keto sulfones (review)

Rhodium(II)-Catalyzed Reaction of Iodonium Ylides with Conjugated Compounds: Efficient Synthesis of Dihydrofurans, Oxazoles, and Dihydrooxepines

Αντιδράσεις Των Ιωδο Υλιδίων Β-Δισουλφονών Και Β-Δικετονών

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