Understanding the π-facial diastereoselectivity in the addition of chiral diaminophosphino(silyl)carbenes to activated olefins

Illa, Ona; Bagan, Xavier; Baceiredo, Antoine; Branchadell, Vicenç; Ortuño, Rosa M.

doi:10.1016/j.tetasy.2008.10.021

Cited by 7 publications

(2 citation statements)

References 34 publications

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“…Irradiation of H 1′ led to the observation of 2.0 and 1.8% NOE’s, in 5 -cis and 5 -trans, respectively, with one of the methylenic protons which was, accordingly, assigned as H 3′b . The stereochemical outcome of this reaction is similar to that reported by Baceiredo et al, where addition of phosphinosilyl carbenes to acrylate resulted in the stereoselective formation of the cis product …”

Section: Resultssupporting

confidence: 86%

Experimental and Computational Exploration of Indolizinyl Carbene Generation. A Route to Biindolizines

et al. 2011

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In previous work, (E)-2-enynyl pyridines were reported to yield indolizinyl singlet carbenes through base-catalyzed E/Z isomerization followed by a 5-exo-dig pseudocoarctate cyclization. We report herein that in the presence of ethyl acrylate these carbenes undergo stereoselective cis-cyclopropanation due mainly to electrostatic interactions in the transition state. The scope of this carbene generation scheme has been further explored through the preparation of a symmetric bis(pyridylenyl)alkyne which spontaneously furnished the biindolizine core in a one-pot reaction. Computational characterization of this transformation suggests a highly asynchronous double cyclization.

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Section: Resultssupporting

confidence: 86%

Experimental and Computational Exploration of Indolizinyl Carbene Generation. A Route to Biindolizines

et al. 2011

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“…In the 31 P{ 1 H} NMR spectrum, the phosphorus atom of the phosphine oxide moiety resonates at d = 37.8 ppm. [15,16] In the 1 H NMR spectrum, the two diastereotopic hydrogen atoms of the methylene group appear as a set of two doublets of doublets at d = 2.31 ( 2 J HH = 13.8, 2 J HP = 16.2 Hz) and 2.69 ppm ( 2 J HH = 13.8, 2 J HP = 22.2 Hz) in a 1:1 integration ratio.…”

Section: Resultsmentioning

confidence: 99%

Chemical Behaviour of a Prototype Boryl(phosphino)carbene

Lavigne¹,

Maerten²,

Alcaraz³

et al. 2013

Chemistry A European J

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We recently disclosed the synthesis of a novel "push-pull" boryl(phosphino)carbene. To determine the influence of this substitution pattern on the chemical behaviour, a study into the reactivity of the prototype (1) of this new family of B(sp(2))-substituted phosphinocarbenes was undertaken. Carbene 1 exhibits one of the most common intramolecular rearrangements of singlet carbenes, involving a 1,2-mesityl shift, and typical [2+1] cycloaddition reactions with electron-poor acrylonitrile. A pronounced α,β-ambiphilic character was also shown by the reaction of 1 with benzaldehyde, leading to phosphorylalkene 4. Due to its specific electronic properties, carbene 1 also exhibits unprecedented reactivity with chloroacrylonitrile, enabling the formation of bicyclo[1.1.0]phosphetanium salt 6 and borylcyclopropene 9, which have been fully characterised by NMR spectroscopy and X-ray crystallography.

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