The reaction of triphenylmethylhalophosphines with tetrachloro-orthobenzoquinone: Oxidation?isomerization?dehydrohalogenation

Plack, Volker; Goerlich, Jens R.; Thnnessen, Holger; Jones, Peter G.; Schmutzler, Reinhard

doi:10.1002/(sici)1098-1071(1999)10:4<277::aid-hc3>3.0.co;2-5

Cited by 7 publications

(1 citation statement)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2 In the following, we report our first experiments on reactions of 1a and 1b with cyclopentadiene and with tetrachloro-o-benzoquinone (TOB), both of which are typical reagents for [2+4] cycloadditions to phosphaalkenes. [3][4][5] TOB also adds oxidatively to other shortlived or persistent compounds of low-coordinated phosphorus, [6][7][8] and-in a [4+1] fashion-to P(σ 3 λ 3 )-compounds, 6,[9][10][11][12] 2 C=P-E-PR 2 (R = tBu, iPr) with cyclopentadiene, the initially formed endo-isomers usually rearranged to the more stable exo-isomers within 24 h 4 ; we therefore assume that both diastereomers of 2a and 2b were isolated as the exo,exo-isomers, as depicted in Scheme 1.…”

Section: Diastereoselective Reactions Of Sulfur-and Selenium-bridged mentioning

confidence: 99%

Diastereoselective Reactions of Sulfur- and Selenium-Bridged Bisphosphaalkenes with Tetrachloro-o-benzoquinone

Gust

Mont

Schmutzler

et al. 2009

Phosphorus, Sulfur, and Silicon and the Related Elements

Self Cite

View full text Add to dashboard Cite

Se) react as bifunctional phosphaalkenes with two equivalents of cyclopentadiene and of tetrachloro-o-benzoquinone (TOB), furnishing 2a and 2b from double [2+4] cycloaddition reactions of the diene and 3a and 3b from the reactions of TOB with the P=C double bonds. The phosphanorbornane-related chalcogenophosphinous anhydrides 2a and 2b are obtained as pairs of isomers, whereas the reactions with TOB proceed diastereoselectively. X-ray crystallographic data confirm that bisdioxaphospholene-related 3b consists of a mixture of (RR) and (SS) enantiomers.A third equivalent of TOB can be added oxidatively to one phosphorus atom of 3a and 3b, furnishing the spirocyclic compounds 6a and 6b with P(σ 3 λ 3 )-E-P(σ 5 λ 5 ) connectivity. 3a and 6a are configurationally stable at room temperature, whereas the selenium derivatives 3b and 6b undergo slow isomerisation in solution.

show abstract