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Kozhushkov, Sergei I.; Brandl, Melanie; Meijere, Armin de

doi:10.1002/(sici)1099-0690(199808)1998:8<1535::aid-ejoc1535>3.3.co;2-g

Cited by 12 publications

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“…[26c,35a,36] In full accord with this, the addition of thiols 80aϪh to the double bond of bicyclopropylidene (2) in benzene proceeds rapidly at 20 to 75°C, in the absence of catalysts or radical initiators, to give products 81aϪh almost quantitatively with complete retention of both three-membered rings (Scheme 15). [37] The addition of thiols to the n-alkylbicyclopropylidenes 7eϪg does not proceed stereoselectively, although in all cases the thioester function adds to the double bond with retention of the cyclopropane ring to give interesting new compounds containing bicyclopropyl fragments. [37] Apparently, the intermediate 1-(1Ј-alkylthiocyclopropyl)cyclopropyl radicals in this radical addition to 2 undergo ring opening far less rapidly than ordinary cyclopropylmethyl radicals.…”

Section: Electrophilic and Radical Additionsmentioning

confidence: 99%

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An Evolving Multifunctional Molecular Building Block: Bicyclopropylidene

2000

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The elucidation of the chemistry of the highly strained and unusually tetrasubstituted alkene bicyclopropylidene (2), has proved to be fruitful, both with respect to synthetic applications as a multifunctional C 6 building block and for the understanding of certain reaction principles. The different, and steadily improved, methods developed over the last thirty years for the preparation of this unusual alkene, and the more recent methods for the synthesis of functionally substituted as well as spirocyclopropanated derivatives, are presented. The rich chemistry of bicyclopropylidene, beginning with its well-known thermal rearrangement and dimeriz-[a] and books. His scientific achievements have been published in over 420 original publications, review articles, and chapters in books. His current research interests include the development of new cascade reactions for the efficient construction of complex skeletons and new small-ring building blocks to be applied in the synthesis of natural and nonnatural compounds, new highly strained polycyclic compounds with interesting properties, as well as the development of new synthetic methodology based on metal-mediated and -catalyzed transformations of organic compounds.

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Section: Electrophilic and Radical Additionsmentioning

confidence: 99%

“…[35] )Scheme 15. Radical addition of thiols and dithiols 80 to bicyclopropylidene (2) (see ref [37]. )…”

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An Evolving Multifunctional Molecular Building Block: Bicyclopropylidene

2000

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“…Thiophenol (13a) reacted readily with 1 both in C 6 D 6 , as published, [12] and in CD 3 CN to afford 26 quantitatively Scheme 5. Radical addition of thiophenol (13a) to 1 in benzene [12] or acetonitrile (Scheme 5).…”

Section: Resultsmentioning

confidence: 95%

“…[12] They also reported that the addition is suppressed in the presence of [Pd(OAc) 2 ]. This could explain why only traces of thioethers like 26 were observed in the 3 and Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…Radical addition of thiophenol (13a) to 1 in benzene [12] or acetonitrile (Scheme 5). However, when the same reaction was performed in CH 3 CN in the presence of K 2 CO 3 , CO and a Pd catalyst only traces of 26 were detected, whilst in the absence of K 2 CO 3 26 was isolated in 20% yield indicating that both the Pd catalyst and K 2 CO 3 are important for the outcome of the cascade reaction.…”

Section: Resultsmentioning

confidence: 99%

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Multicomponent Queuing Cascades of Bicyclopropylidene, Carbon Monoxide and Aryl Iodides or Aryl Thiols

2002

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Structural Parameters and Electronic Interactions in Substituted 1,1-Diethynylcyclopropanes − An Experimental Study

Meijere

Kozhushkov

Boese³

et al. 2002

Eur. J. Org. Chem.

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Keywords: Alkynes / Conjugation / Diethynylcyclopropanes / Small ring systems / Structure elucidation 1,1-Bis(trimethylsilylethynyl)cyclopropane (4) and dimethyl 3,3Ј-(1,1-cyclopropanediyl)bis(2-propynoate) (5) have been prepared by silylation of the known 1-(bromoethynyl)-1-(trimethylsilylethynyl)cyclopropane (7) and by double carboxylation of 1,1-diethynylcyclopropane (3) followed by esterification, in 91 and 74% overall yields, respectively. 7,7-Diethynyldispiro[2.0.2.1]heptane (6) has been synthesized from ethyl dispiro[2.0.2.1]heptane-7-carboxylate (9) by a ten-step sequence in 41% overall yield. Upon UV irradiation, the diacetylene 4 underwent ethylene extrusion, and the resulting bis(trimethylsilylethynyl)carbene dimerized with electron reorganization to give 1,4,8-tris(trimethylsilyl)-3-(trimethylsilylethynyl)oct-3-ene-1,5,7-triyne (20) (24% yield). X-ray crystal structure analyses of 4, 5, and 6 revealed strong electronic

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Cited by 12 publications

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An Evolving Multifunctional Molecular Building Block: Bicyclopropylidene

An Evolving Multifunctional Molecular Building Block: Bicyclopropylidene

Multicomponent Queuing Cascades of Bicyclopropylidene, Carbon Monoxide and Aryl Iodides or Aryl Thiols

Structural Parameters and Electronic Interactions in Substituted 1,1-Diethynylcyclopropanes − An Experimental Study

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