214707-56-9Relevant academic research and scientific papers
Photochemical C(sp)-C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM-CP
Boback, Nico,Coles, Nathan T.,Dittrich, Birger,Frost, Daniel S.,G?rlich, Tim,Jones, William D.,Müller, Christian,Müller, Peter
, p. 19365 - 19373 (2021/11/26)
The photochemical activation of the C(sp)-C(sp2) bond in Pt(0)-ν2-aryl-phosphaalkyne complexes leads selectively to coordination compounds of the type LnPt(aryl)(CP). The oxidative addition reaction is a novel, clean, and atom-economic route for the synthesis of reactive terminal Pt(II)-cyaphido complexes, which can undergo [3 + 2] cycloaddition reactions with organic azides, yielding the corresponding Pt(II)-triazaphospholato complexes. The C-C bond cleavage reaction is thermodynamically uphill. Upon heating, the reverse and quantitative reductive elimination toward the Pt(0)-phosphaalkyne-π-complex is observed.
Organophosphorus compounds, 138: 3,5-dimesityl-1,2,4-oxadiphosphole - Synthesis and reactivity of a novel heterocycle
Mack, Andreas,Bergstr??er, Uwe,Rei?, Guido J.,Regitz, Manfred
, p. 587 - 595 (2007/10/03)
The first synthesis of a 1,2,4-oxadiphosphole 6 has been achieved by vacuum thermolysis of mesitylphosphaalkene 5. The novel heterocycle 6 exhibits an enormous potential for cycloaddition reactions, which predominantly proceed selectively at low temperatures. Compound 6 undergoes addition with two equivalents of phosphaalkynes 10 by a [4+2] cycloaddition/homo Diels-Alder reaction sequence to form novel oxatetraphosphadeltacyclenes 12 and 13. Tetrachloro-o-benzoquinone (14) undergoes a selective [4+1] cycloaddition with 12 and 13 leading to the spirocyclic products 15 and 16 containing λ5-phosphorus atoms. Treatment of the oxadiphosphole 6 with dimethyl acetylenedicarboxylate (17) provides the first access to a 1,2-oxaphosphole 18, which is formed after an initial [4+2] cycloaddition followed by a retro Diels-Alder reaction. An unexpected reaction of 6 is observed with tri-tert-butylazete (20) furnishing a new polycyclic system (→ 21).
Organophosphorus compounds; 129. Mesitylphosphaacetylene: Synthesis and reactivity studies of a new phosphaalkyne
Mack, Andreas,Pierron, Elke,Allspach, Thomas,Bergstra??er, Uwe,Regitz, Manfred
, p. 1305 - 1313 (2007/10/03)
Mesitylphosphaacetylene (1b) has been synthesized by AlCl3 initiated elimination of bis(trimethylsilyl) ether from the phosphaalkene 2b. This new phosphaalkyne undergoes [3+2] cycloaddition reactions with diazo compounds (→ 6a,b), azides (→ 8a-c), and nitrile oxides (→ 10a,b) to yield five-membered heterocyclic products. The mesoionic reaction partners 11 and 13 react with 1b under elimination of CO2 and COS, respectively, to furnish the 1,3-aza- and 1,3-thiaphospholes 12 and 14. Reaction of 1b with buta-1,3-diene leads to the diphosphatricyclooctene 18; it has been shown that the 1-phosphacyclohexa-1,4-diene 15 (characterized by an X-ray structure analysis of its W(CO)5 complex 17) is an intermediate in the multistep reaction. Moreover, 1b has been characterized by Diels-Alder reactions with the cyclobutadiene 19 and the azacyclobutadiene 21 to afford the Dewar hetarenes 20 and 22.
