Phenyliodonium bis(phenylsulfonyl)methylide, a new hypervalent iodonium ylide

Hadjiarapoglou, Lazaros P.; Spyroudis, Spyros; Varvoglis, Anastasios

doi:10.1021/ja00310a072

Cited by 63 publications

(37 citation statements)

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“…Alkylation of thioureas 183, followed by deprotonation of the isothiuronium salts 184, proved to be a versatile route to 185. [252] Alternatively, oxiranes 186 (R ϭ CF 3 , [253] CN [254] ), diazo compounds 187 [255] and 188, [256] and iodonium ylides 189 (A ϭ RCO, [257] PhSO 2 [258] ) have been employed in methylenetransfer reactions with 183. Recently, X-ray crystal structures of 190 have been obtained.…”

Section: Betainesmentioning

confidence: 99%

Carbene Complexes of Nonmetals

Kirmse

2005

Eur J Org Chem

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Electrophilic carbenes accept a variety of n‐ and π‐donors. The products range from persistent ylides to matrix‐isolated xenon complexes. Ylides can be viewed as carbene complexes if they regenerate carbenes thermally or undergo concerted methylene transfer reactions. According to these definitions, the present review focuses on oxonium and iodonium ylides. Transient π‐complexes appear to be involved in addition reactions of carbenes with arenes (but not with alkenes). Nucleophilic carbenes form adducts with Lewis acids which are, for the most part, stable and have been well characterized structurally. Only recently attention has been directed to reversible systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Betainesmentioning

confidence: 99%

Carbene Complexes of Nonmetals

Kirmse

2005

Eur J Org Chem

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“…To our knowledge this is the first example of a CH insertion reported for a Rh"-catalyzed decomposition of a iodonium ylide. Although formal insertion products were reported as by-products from decomposition reactions of iodonium ylides, [14] [33] their origin is unclear, since they could also be formed via ring opening of cyclopropanes. The yield of the reaction with 13c was, however, lower than that achieved with 13b.…”

Section: Rel To Styrene (3a)mentioning

confidence: 99%

Carbenoid Reactions in Rhodium(II)‐Catalyzed Decomposition of Iodonium Ylides

Müller

Fernández

1995

Helvetica Chimica Acta

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The intermediacy of metallocarbenes in decomposition reactions of iodonium ylides with [Rh,(OAc),] was established by comparison with reactions of the corresponding diazo compounds. The sensitivity of the Rh"-catalyzed intermolecular cyclopropane formation from substituted styrenes and bis(methoxycarbonyl)(phenyliodono)methanide (la) or dimethyl diazomalonate (lb) is identical. The Hummerr plot (with a ' ) has a slope of -0.47. Iodonium ylides and diazo compounds afford the same products in [Rh,(OAc),]-catalyzed cyclopropane formations, cycloadditions, and intramolecular CH insertions, and exhibit the identical selectivity in intramolecular competitions for cyclopropane formation and insertion. The intramolecular CH insertion of the ylide ZOe, when carried out in the presence of a chiral catalyst ([Rh2{(-)-(S)-ptpa}4]), results in formation of 21a having an ee of 67%, identical to the ee obtained with the diazo compound 20b.Introduction. -The decomposition of diazoketones and diazoesters in the presence of chiral transition-metal catalysts has a remarkable potential for asymmetric catalysis [I]. Cu-Based catalysts [2-51 found successful applications in intermolecular cyclopropane formation with olefins, while chiral Rh"-complexes provided products of intramolecular cyclopropane formation [6], CH insertion [7-91, and intermolecular cyclopropene formation of acetylenes [lo] having enantiomeric excesses in the range of 95% or more. The major drawback of these reactions is the requirement of diazo compounds as precursors which are potentially explosive, toxic, or/and carcinogenic [ 1 11.The transition-metal-catalyzed decomposition of diazo compounds leads to metallocarbenes which are not isolable, but transfer the carbene moiety to a suitable acceptor molecule or to an appropriate reactive site within the metallocarbene [l]. Thus, the use of diazo compounds might be avoided if it were possible to generate the metallocarbenes from other precursors. This investigation deals with the use of iodonium ylides [12-151 as precursors for metallocarbenes in view of their application to asymmetric catalysis.The photochemical and transition-metal-catalyzed decomposition of iodonium ylides such as l a (bis(methoxycarbonyl)(phenyliodono)methanide) [

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“…It was also noticed that both 4a and 4b are unstable. For example, the decomposition of PhI+--C(PhS0)2 occurred during recrystallization, and the compound had to be stored at -10°C [6,7]. Compound 3, however, is more stable.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, Varvoglis reported a neu route for the synthesis of a dihalobis(phenylsulfony1)-methane by the reaction of 4b with an N-halosuccinimide [6,12] The dibromides, (CF3SOJzCBr2 and 02)S(CFJ3S02C'Br2, could be prepared by the reaction of 3a or 3c with bromine in high yield (89%, for example):…”

Section: Figurementioning

confidence: 99%