Photochemistry of Bis(sulfonyl)diazomethanes

Sander, Wolfram; Strehl, Anja; Winkler, Michael

doi:10.1002/1099-0690(200110)2001:20<3771::aid-ejoc3771>3.0.co;2-0

Cited by 34 publications

(23 citation statements)

References 34 publications

(14 reference statements)

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“…Wolff rearrangements of α-diazosulfones Irradiation of bis(phenylsulfonyl)diazomethane (881) in an argon matrix at 10 K generated the sulfonylsulfene 882. [619] The intervening carbene could not be scavenged under matrix conditions although carbene-derived products were obtained in solution. [118b, 619,620] Laser flash photolysis of 881 in acetonitrile led to detection of the sulfene 882 and the sulfene ylide 883 formed upon sulfene trapping by pyridine (Nu ϭ pyridine; k f ϭ 4·10 6  Ϫ1 s Ϫ1 ).…”

Section: α-Diazophosphane Oxides -Phosphinates and Related Substratesmentioning

confidence: 99%

“…[619] The intervening carbene could not be scavenged under matrix conditions although carbene-derived products were obtained in solution. [118b, 619,620] Laser flash photolysis of 881 in acetonitrile led to detection of the sulfene 882 and the sulfene ylide 883 formed upon sulfene trapping by pyridine (Nu ϭ pyridine; k f ϭ 4·10 6  Ϫ1 s Ϫ1 ). [621] The kinetics of competitive sulfene quenching indicate that 882 reacts rapidly with anions (k ϭ 10 5 Ϫ10 7  Ϫ1 s Ϫ1 ) but rather slowly with alcohols and water (k Ͻ 10 3  Ϫ1 s Ϫ1 ).…”

Section: α-Diazophosphane Oxides -Phosphinates and Related Substratesmentioning

confidence: 99%

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100 Years of the Wolff Rearrangement

2002

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The conversion of α‐diazo ketones into ketenes, and products derived therefrom, was discovered by Wolff in 1902. Major applications of the Wolff rearrangement, such as the Arndt−Eistert reaction (homologation of carboxylic acids) and the ring contraction of cyclic ketones, have been with us for some while. Nevertheless, substantial progress has been made recently. The reaction mechanism has been explored by means of matrix isolation, time‐resolved spectroscopy, and computation. Full retention of configuration of the migrating group has been established by using enantioselective chromatography. The Arndt−Eistert reaction has witnessed a renaissance in the field of natural products, in particular β‐amino acids and β‐peptides. Ring‐contracting Wolff rearrangements and ketene cycloadditions have been applied in syntheses of increasingly complex, biologically active target molecules. These accomplishments, as well as unsolved problems, are addressed in the present review. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: α-Diazophosphane Oxides -Phosphinates and Related Substratesmentioning

confidence: 99%

Section: α-Diazophosphane Oxides -Phosphinates and Related Substratesmentioning

confidence: 99%

100 Years of the Wolff Rearrangement

2002

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“…3 According to our calculations, the energy of equilibrium structures of CO molecule and two separated radicals 4 and 5 is by 76 kcal/ mole lower than the energy of the trans-oxathiirine oxide. In fact, even minor deformations of PhSC bending angle ͑Fig.…”

Section: Modeling Of the Products Of Photoinduced Decomposition Ofmentioning

confidence: 72%

“…3 To clarify this problem, we performed additional modeling of possible products of DPSD decomposition. 3 for singlet bis ͑methylsulphonyl͒ carbene within both MP2 / 6-31G͑d , p͒ and B3LYP/ 6-31G͑d , p͒ approximations, the carbene itself does not correspond to the true minimum on the PES, being, in fact, the first-order saddle point, while the true minima are cis and trans isomers of the corresponding oxathiirine oxide. 10 and are numbered according to their numbers used throughout the rest of the article.…”

Section: Modeling Of the Products Of Photoinduced Decomposition Ofmentioning

confidence: 99%

Remarkably efficient acid generation in chemically amplified resist from quantum chemistry modeling

Granovsky

Bochenkova

Suetin³

et al. 2007

Journal of Vacuum Science &Amp; Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena

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Articles you may be interested inHigh sensitivity nonchemically amplified molecular resists based on photosensitive dissolution inhibitorsThe authors apply methods of quantum chemistry to obtain information on the equilibrium geometrical structure, IR and UV spectra of the photoacid generator ͑PAG͒ di͑phenylsulphonyl͒ diazomethane ͑DPSD͒ and products of its photoinduced decomposition, and UV spectra of polyhydroxystyrene ͑PHOST͒ and poly͑4-t-butoxycarbonyloxystyrene͒ ͑PTBOCST͒, and to characterize a viable alternative path for photoinduced decomposition of DPSD in PHOST-like resists. In contrast with previously published sulphone-based chemistry, the newly suggested path for acid generation results in formation of up to two acid molecules per single PAG molecule. The theoretical results are quantitatively compared with available experimental data.

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“…Sulfur dioxide and PhSO 2 SPh are decomposition products obtained from the labile bis(phenylsulfonyl)methylene. 1,10 All the reactions of the ylides 1 with the a,b-enones 3 were run with an excess of the a,b-enone until complete consumption of the ylide, as indicated by the dissolution of the heterogeneous mixture to a clear solution (Scheme 2). Furthermore, all the reactions of ylide 1a with the a,b-enones 3 were carried out in the presence of a catalytic amount of Rh 2 (OAc) 4 to shorten the reaction time.…”

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confidence: 99%

[3+2] Cycloaddition of Phenyliodonium Bis(arylsulfonyl)methylides with α,β-Enones

Adam¹,

Gogonas²,

Nyxas³

et al. 2007

Synthesis

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The [3+2] cycloaddition of phenyliodonium bis(arylsulfonyl)methylides to a,b-enones affords exclusively trans,transconfigured 1-(arylsulfonyl)-2-aroyl-3-arylindanes. The initial electrophilic attack of the iodonium ylide on the alkenyl double bond of the chalcone, followed by cyclization of the dipolar species, and subsequent ejection of iodobenzene and sulfur dioxide, stereoselectively affords the indane cycloadduct.Phenyliodonium bis(arylsulfonyl)methylides 1 1 constitute a class of compounds with unique properties among the iodonium ylides (Scheme 1). Under photochemical or Cu(acac) 2 -catalyzed thermal activation, an iodonium bis(sulfonyl)methylide reacts with simple alkenes to give the corresponding cyclopropanes, 1 and with various heteroatom nucleophiles to provide new ylides, 1,2 presumably through a carbene (or carbenoid) pathway. At room temperature, however, an unusual [3+2] cycloaddition occurs, in which a 1,2,3-trisubstituted indane is produced. For example, various acyclic 1,2-disubstituted alkenes, either Z-or E-configured, lead to the trans,trans-indane cycloadducts, 3 whereas cyclic alkenes yield the cis,cisstereoisomers 4 (Scheme 1). This reactivity is explained by postulating an initial electrophilic attack of the ylide on to the alkenyl double bond, followed by cyclization to the [3+2] cycloadduct. This perplexing chemical behavior poses the mechanistic question, whether an iodonium bis(sulfonyl)methylide reacts initially as a nucleophile in view of its stabilized carbanionic center, as an electrophile through its positively charged iodonium center, and/or as a carbene (or carbenoid) precursor by cleavage of iodobenzene. The incentive of the present study was to distinguish between these mechanistic options by examining the reaction of the iodonium bis(sulfonyl)methylides with a,b-enones.In a,b-enones, which are widely distributed in nature, the carbonyl group decreases the electron density of the olefinic double bond. Thus, while the carbonyl and the b-ethylenic carbon atoms are activated toward nucleophilic attack, the alkenyl double bond should be less susceptible to electrophilic attack. Nevertheless, it is well known that a,b-enones react with a variety of stable ylides to yield cyclopropanes; 5 adducts are formed as well with rather mild electrophiles 6 and diazo compounds. 7 If the iodonium ylide should react initially as a nucleophile, then attack at the b-ethylenic carbon atom of the a,b-enone would produce an enolate, which on subsequent intramolecular ring closure with ejection of iodobenzene should afford a cyclopropane product. Such a reaction type is known as a Michael-induced ring closure, 5 observed in the reaction of a,b-enones with sulfur and phosphorus ylides. The same cyclopropane cycloadduct would also result if the iodonium bis(sulfonyl)methylide should serve as a carbene (or carbenoid) source. In contrast, if the iodonium bis(sulfonyl)methylide should react initially as an electrophile by attacking the a-ethylenic carbon atom of the a,b-enone, indane derivatives should b...

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Photochemistry of Bis(sulfonyl)diazomethanes

Cited by 34 publications

References 34 publications

100 Years of the Wolff Rearrangement

100 Years of the Wolff Rearrangement

Remarkably efficient acid generation in chemically amplified resist from quantum chemistry modeling

[3+2] Cycloaddition of Phenyliodonium Bis(arylsulfonyl)methylides with α,β-Enones

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