Sterisch kontrollierte, metallinduzierte Synthese eines 1‐Thia‐2,4‐diphosphols

Lindner, E.; Huuse, Cornelius; Mayer, Hermann A.; Kemmler, M.; Fuwzi, Riad; Steimann, Manfred

doi:10.1002/ange.19931051030

Cited by 13 publications

(1 citation statement)

References 13 publications

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“…The replacement of two CH units in thiophene A by phosphorus atoms formally leads to four isomeric thiadiphospholes ( B − E ). Only representatives of the types D and E are known, namely the poorly characterized 4,5-bis(trifluoromethyl)-1,2,3-thiadiphosphole (type E ) and four 1,2,4-thiadiphospholes of the type D (R 1 = Me 3 SiS, R 2 = Me 3 Si; R 1 = R 2 = Me 3 SiO; R 1 = R 2 = Ph; R 1 = R 2 = t Bu , ). Compound 8a is the first example of a 1,3,4-thiadiphosphole (type C ).…”

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confidence: 99%

Transition-Metal-Substituted Acyl Phosphanes and Phosphaalkenes. 33.¹ Transition-Metal-Substituted Arsaalkenes. 3.² Reactivity of Metallodisilylphosphanes and -arsanes (η⁵-C₅Me₅)(CO)₂M−E(SiMe₃)₂ (M = Fe, Ru; E = P, As) toward Carbon Disulfide. Formation of Metallophosphaalkenes, Metalloarsaalkenes, and 1,3,4-Thiadiphospholes

et al. 1997

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Reaction of (η5-C5Me5)(CO)2FeP(SiMe3)2 (4a) with carbon disulfide afforded the unstable metallophosphaalkene (η5-C5Me5)(CO)2Fe−PC[SSiMe3]2 (5a), which decomposed to the doubly metalated 1,3,4-thiadiphosphole 8a by extrusion of bis(trimethylsilyl)sulfide. The transient metallophosphaalkene 5a was intercepted as the isolable [(CO)5Cr]-adduct 6a by treatment with [(Z)-cyclooctene]Cr(CO)5. Similarly, the metallodisilylarsanes (η5-C5Me5)(CO)2M−As(SiMe3)2 (M = Fe, Ru) (11a,b) were converted to stable metalloarsaalkenes 12a,b by exposure to CS2. Pentacarbonylchromium complexes 13a,b were accessible by reaction with [(Z)-cyclooctene]Cr(CO)5. The X-ray structure analysis of 13a revealed the molecule as the first η1-arsaalkene complex.

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Section: Resultsmentioning

confidence: 99%

Transition-Metal-Substituted Acyl Phosphanes and Phosphaalkenes. 33.¹ Transition-Metal-Substituted Arsaalkenes. 3.² Reactivity of Metallodisilylphosphanes and -arsanes (η⁵-C₅Me₅)(CO)₂M−E(SiMe₃)₂ (M = Fe, Ru; E = P, As) toward Carbon Disulfide. Formation of Metallophosphaalkenes, Metalloarsaalkenes, and 1,3,4-Thiadiphospholes

et al. 1997

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3,5-Dimesityl-1,2,4-oxadiphosphole – Synthesis and Reactivity of a Novel Heterocycle

et al. 1999

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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).

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Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCI. Insertion of Activated Alkynes and Sulfur into the P‐P Bond of Diphosphamolybdacyclopropanes

et al. 1995

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The insertion of the alkynes ZC=CZ (2a-i) [Z = C02R: R = Me (a), Et (b), nPr (c), iPr (a), nBu ( e ) , tBu (f), neo-Pent ( g ) , cyc-Hex (h); Z = CF, (i)] into the P1-P2 bond of the diphosphamolybdacyclopropane (if-C5H5)(OC)2hiio-P1Ph2-fi2Mes (1) (Mes = 2,4,6-trimethylphenyl) results in the formation of the diphosphamolybdacyclopentenes ( T~~-C~H~) ( O C )~-hiio-P1Ph2-CZ=CZ-P2Mes (3a-i). According to an X-ray structural analysis, 3a crystallizes in the space group P2,lc with the mesityl function at P2 and the cyclopentadienyl fragment at the metal atom on the opposite side of the planar five-membered ring. The same orientation is found in solution by NMR experiments (NOE; 2D 'H, 13C HETCOR). Kinetic investigations confirm that the rate constants decrease in the sequence R = Me > Et > nPr > isoProp > Cy > nBu > neo-Pent > tBu. The second-order reaction and the strongly negative activation entropy which was determined in the case of the reaction 1 + 2e -+ 3e are consistent with a nucleophilic attack of P2 at one of the triply bonded carbon atoms of the alkyne. The reaction of 3a, h with sulfur affords the diastereomeric compounds (q5-C5Hs)(OC)2kfo-P1-Ph2-CZ=CZ-PZ(S)Mes (4a, h). An X-ray structural analysis of the heterocycle 4h, which crystallizes in the space group P i , shows the presence of the enantiomeric pair SWRS. C5H5)(OC)2bho-P1Ph2-S-P2(S)Mes-$ (6) which crystallizesin the space group Pi. The five-membered ring in 6 has an envelope conformation. Upon thermally induced cleavage of the P2S2Mes fragment from 6 the three-membered ring (q5-C5H5)(OC)2hiio-P1Ph2-$ (?) is formed as the final product.The transition metal-catalyzed or -mediated cyclooligomerization of alkynes with heteroalkynes offers a well developed method for the preparation of four-and six-membered organic heterocycle~ [~~~]. Recently, it could be demonstrated that the P-S group in thiaphosphametallacyclopropanes behaves like a heteroalkyne because of similar covalent radii and comparable electronegativities of the phosphorus and sulfur atomL4]. It is therefore suitable for a metal-mediated cyclo-cotrimerization with alkynes. Starting from the threemembered heterocycles [ M W , we obtained regiospecifically substituted thiophenesL5I, phosphole and furansL7I, respectively, which are obtained by oxidative or hydrolytic degradation of the resulting metallabicycloheptadienes. The latter were formed via the intermediately occurring thiaphosphametallacyclopentadienes which could be Between sulfur and the PR fragment exists an isolobal relation. Meanwhile we are able to make accessible heterocycles of the type [T61-PR:-PR2r9-101. Since the [R2PS]-and [R$PPR2]-systems exhibit similar structural features, we were interested in the question whether the phosphorus analog also displays alkyne-like properties. In principle, an alkyne may be inserted into the Mo-PR:, Mo-PR2 or intothe R&P-PR2 bond of the above-mentioned three-membered heterocycle. In a communication["] lately we reported on the insertion of dimethyl acetylenedicarboxylate into the P-P bond o...

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Sterisch kontrollierte, metallinduzierte Synthese eines 1‐Thia‐2,4‐diphosphols

Cited by 13 publications

References 13 publications

3,5-Dimesityl-1,2,4-oxadiphosphole – Synthesis and Reactivity of a Novel Heterocycle

Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCI. Insertion of Activated Alkynes and Sulfur into the P‐P Bond of Diphosphamolybdacyclopropanes

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