[4 + 2] Cycloadditions between 2H-phospholes and alkenes. Synthesis and properties of 1-phosphanorbornenes

Goff, Philippe Le; Mathey, François; Ricard, Louis

doi:10.1021/jo00281a013

Cited by 31 publications

(19 citation statements)

References 3 publications

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“…[204] The conversion of the parent 1H-into 2H-phosphole requires a very low activation enthalpy of approximately 16 kcal mol À1 . The 2H-phosphole products can be trapped by alkynes, [202] alkenes, [205] dienes, [202] and aldehydes [Eq. (74)].…”

Section: Aromatic Systemsmentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

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Section: Aromatic Systemsmentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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“…Mathey also described the reversible formation of a series of 2H-phosphole cycloadducts [6,9,18]. It is the novel and quite surprising observation of ours that precursor 6 was also dedimerized on treatment at 0…”

Section: Resultsmentioning

confidence: 64%

“…At 150 • C, the dimer was decomposed to two units of 2H-phosphole (2a and 5) (Scheme 2) entering into reaction with tolane. Mathey also described the reversible formation of a series of 2H-phosphole cycloadducts [6,9,18]. It is the novel and quite surprising observation of ours that precursor 6 was also dedimerized on treatment at 0 • C with hydrogen peroxide to afford phosphole oxide intermediate 7 leading spontaneously to its dimer 8 (Scheme 3).…”

Section: Resultsmentioning

confidence: 84%

“…For phenylphospholes, lacking aromaticity due to the pyramidal character of the phosphorus atom, the overlap between the -dienic system and theorbital of the exocyclic P Ph bond promotes the migration of the Ph-group. The 2H-phospholes generated at 160 • C were trapped by alkynes and alkenes or dimerized in [4 + 2] cycloadditions to yield 1phosphanorbornene derivatives [3][4][5][6][7]. An important practical application of the reaction under discussion is the synthesis of 2,2 -bis-(1-phosphanorbornadienyl) (BIPNOR) which is an efficient biphosphine for asymmetric catalysis [8].…”

Section: Introductionmentioning

confidence: 99%

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2,4,6‐Trialkylphenyl‐2H‐phospholes from slightly aromatic 1H‐phospholes and their use in [4 + 2] cycloaddition reactions

Keglevich

Farkas

Imre

et al. 2003

Heteroatom Chemistry

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“…When a trapping reagent (inert toward phosphorus lone pairs) is added to the equilibrium mixture of Scheme 23.17, then 2H-phosphole (F) is efficiently trapped before any further evolution. These reagents include MeOH, non-activated alkynes, conjugated dienes [58], alkenes [59] and aldehydes (Scheme 23.21) [60].…”

Section: [15]-sigmatropic Shiftsmentioning

confidence: 99%

Phosphorus Heterocycles

Mathey

2011

Modern Heterocyclic Chemistry

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Figure 23.1 The three isomers of the phosphole system (A-C) and the phospholide ion (D).2072j 23 Phosphorus Heterocycles shown with 1-alcoxyphospholes, which are relatively flat with a negligible delocalization [12]. Contrary to phospholes, the structure of phospholide ions reflects their high aromaticity. For example, the planar 2,3,4,5-tetramethylphospholide with Li(TMEDA) þ as the counterion displays the following parameters [13]: P-C, 1.715 A ; C¼C, 1.396 A ; CÀC, 1.424 A ;

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[4 + 2] Cycloadditions between 2H-phospholes and alkenes. Synthesis and properties of 1-phosphanorbornenes

Cited by 31 publications

References 3 publications

Phospha‐Organic Chemistry: Panorama and Perspectives

Phospha‐Organic Chemistry: Panorama and Perspectives

2,4,6‐Trialkylphenyl‐2H‐phospholes from slightly aromatic 1H‐phospholes and their use in [4 + 2] cycloaddition reactions

Phosphorus Heterocycles

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