Dicoordinated 2H-phospholes as transient intermediates in the reactions of tervalent phospholes at high temperature. One-step syntheses of 1-phosphanorbornadienes and phosphorins from phospholes

Mathey, François; Mercier, François; Charrier, Claude; Fischer, Jean; Mitschler, A.

doi:10.1021/ja00405a058

Cited by 132 publications

(71 citation statements)

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“…As further proof of the intermediacy of 2H-phosphole, methyl-l,3-butadiene, recovering the Diels-Alder product Mathey reports the reaction of the phosphole with 2,3-diwhere the phosphole acts as the dienophile, with addition across the P=C bond (Scheme 2) (4). Further experiments have shown this propensity for 2H-phosphole to act as the dienophile in reactions with conjugated systems (7,8).…”

Section: Phmentioning

confidence: 92%

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Theoretical exammation of the Diels–Alder reaction of 1,3-butadiene with cyclopentadiene and 2H-phosphole

Bachrach¹,

Perriott²

1996

Can. J. Chem.

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All Diels-Alder reactions between 1,3-butadiene and cyclopentadiene or 2H-phosphole have been examined at the MP4SDQJ6-3 lG*//HF/6-31G* level. There is remarkable similarity between the two systems. The thermodynamic product is the bicyclo[4.2.0]nonadiene while the kinetic product is the norbornene product. There is a slight kinetic preference for the endo addition and for the butadiene to be in the s-trans conformation. Except for the case where butadiene is the diene component and addition is endo, the reactions are concerted and synchronous. In these other two cases, the reaction is stepwise with a diradical intermediate.Key words: phosphole, Diels-Alder reaction, topological electron density analysis.RCsumC : On a CtudiC toutes les rkactions de Diels-Alder entre le buta-1,3-dikne et le cyclopentadikne ou le 2H-phosphole au niveau MP4SDQJ6-3 lG*NHF/6-3 lG*. I1 existe une similarit6 remarquable entre les deux systkmes. Le produit thermodynamique est le bicyclo[4.2.0]nonadikne alors que le produit cinCtique est le produit norbornkne. I1 y a une 1Cgkre prCf6rence cinCtique en faveur de I'addition etldo et pour que le butadikne soit dans la conformation s-trans. A l'exception du cas ou le butadikne agit comme butadikne et que I'addition est endo, toutes les rCactions sont concertCes et synchrones. Dans ces deux autres cas, la rCaction se fait par Ctape avec un intermkdiaire diradicalaire.Mots clPs : phosphole, rCaction de Diels-Alder, analyse topologique de la densit6 Clectronique.[Traduit par la rCdaction]

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Section: Phmentioning

confidence: 92%

“…The only applicable experimental result (4) is the reaction shown in Scheme 2, which shows a clear preference for the phosphole to act as the dienophile with addition across its C=P bond. Mathey did report that another minor unidentified compound was produced.…”

Section: This Paper Is Dedicated To Professor Richard F W Bader On mentioning

confidence: 99%

Theoretical exammation of the Diels–Alder reaction of 1,3-butadiene with cyclopentadiene and 2H-phosphole

Bachrach¹,

Perriott²

1996

Can. J. Chem.

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“…[196] The dienic unit of these 1-alkoxyphospholes is extremely reactive, as shown by the examples in Equations (72) and (73). [195,200] When substituted at the phosphorus center by simple sp- [201] or sp 2 -carbon-containing substituents [202] or hydrogen, [203] the reactivity of phospholes is governed by the hyperconjugative interaction favoring the shift of the substituent from phosphorus to the a-carbon atoms of the ring. These concerted [1,5]-sigmatropic shifts leading to 2H-phospholes have been studied from a theoretical standpoint.…”

Section: Aromatic Systemsmentioning

confidence: 99%

“…[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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“…The key finding which is at the basis of this work, is the successful transposition of the 1-phosphanorbornadiene synthesis [7] [8] for the preparation of 2-stannyl-substituted derivatives. Indeed, transiently formed 2H-phospholes regioselectively react with alkynylstannanes to afford the expected bicyclic structure (eq.…”

Section: Resultsmentioning

confidence: 99%

Functionalisation of the 1-Phosphanorbornadiene Structure at the C2 Position by Stille Cross-Coupling Reactions

et al. 1998

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The reaction of alkynylstannanes with 1‐phenyl‐3,4‐dimethylphosphole at 150 °C affords the corresponding 2‐stannyl‐1‐phosphanorbornadienes (2a, b), in fair yield. Oxidation under mild conditions affords the corresponding phosphane oxides (3a, b), whereas more drastic conditions (H2O2, 15% in toluene at 80 °C) induce the oxidative cleavage of the P‐CH2 bond of the bridge to give a bicyclic phosphinate such as 4. Treatement of 4 by iodine leads to a tin → iodine exchange. The X‐ray crystal structure analysis of the resulting 1‐phospha‐2‐oxabicyclo[2.2.2]octa‐5,7‐diene 1‐oxide confirms the functionalisation at the α‐position and the relief of ring strain taking place upon insertion of oxygen into the P‐CH2 bond of the norbornadiene. The 2‐stannyl‐1‐phosphanorbornadiene 1‐oxides (3a, b) readily undergo tin → iodine exchange. The resulting 2‐iodo derivatives (6a, b) can be cross‐coupled with 2‐furyl‐, 2‐thienyl‐, 2‐pyrrolyl‐, phenylethynyl‐, and vinyl‐tributylstannanes to give the corresponding 2‐functional 1‐phosphanorbornadiene 1‐oxides in excellent yields (80‐95%)

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Dicoordinated 2H-phospholes as transient intermediates in the reactions of tervalent phospholes at high temperature. One-step syntheses of 1-phosphanorbornadienes and phosphorins from phospholes

Cited by 132 publications

References 0 publications

Theoretical exammation of the Diels–Alder reaction of 1,3-butadiene with cyclopentadiene and 2H-phosphole

Theoretical exammation of the Diels–Alder reaction of 1,3-butadiene with cyclopentadiene and 2H-phosphole

Phospha‐Organic Chemistry: Panorama and Perspectives

Functionalisation of the 1-Phosphanorbornadiene Structure at the C2 Position by Stille Cross-Coupling Reactions

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