1,4‐Addition of Grignard Reagents to 2,4,6‐Tri‐<i>tert</i>‐butyl‐1,3,5‐triphosphabenzene

Renner, Jens; Bergsträßer, Uwe; Binger, Paul; Regitz, Manfred

doi:10.1002/anie.200250182

Cited by 19 publications

(10 citation statements)

References 22 publications

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“…In this case, the formation of the 5,6-dihydro-1,3,5-triphospha-Dewar-benzene 5 takes place (Scheme 1). 9 Replacing the Grignard reagents 2 by the organolithium compounds 6, similar reactions can be observed. By the use of n-butyllithium 6a and methyllithium 6b, one obtains the corresponding lithium triphosphininuid salts 7, 8 respectively, from the triphosphinine educt 1a and 1b.…”

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confidence: 58%

“…The comparability of the NMR-spectra of the two products delivers a direct proof of the constitution of the novel class of 1l 5 While the addition of Grignard reagents 2 and organolithium compounds 6 to phosphinines 10 and 1,3,5triphosphinines 9 are known now, similar research on diphosphinines is unknown. While the reaction (warming up from -78°C to r.t.) of n-butyllithium (6a) and the 1,3diphosphinine 15a 12 leads to the decomposition of the latter, an unexpected reaction takes place using a Grignard reagent 2 instead of 6a (Scheme 6).…”

Section: Methodsmentioning

confidence: 95%

“…The proposed structure is best proved by the 13 C{ 1 H} NMR of 10c (R 1 = t-Bu, R 2 = R 3 = Me). For the two new introduced methyl groups, only one signal at 9 As one can see, the separation of the P/C-double bonds does not exist in 10c.…”

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confidence: 95%

“…We have now successfully realized the alkylation of the triphosphacyclohexadienids 3a, 7 and 8. Contrary to the product 4 (Scheme 1) of the protonation reaction, 9 the resulting molecules are the novel 1l 5 ,3,5-triphosphinines 10 and 11 (R 1 = t-Bu, CMe 2 Et, respectively), if the reagents are primary alkyl halides (Scheme 3).…”

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Organophosphorus Compounds,Part 171.1λ⁵,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphosphabenzenes

Steinbach¹,

Renner²,

Binger³

et al. 2003

Synthesis

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1,3,5-Triphosphabenzenes 1 react readily with alkyl lithium compounds to give the triphosphininuid salts 7 and 8 through alkylation of one of the phosphorus atoms. Subsequent reaction with primary alkyl halides leads to the formation of 1l 5 ,3,5-triphosphabenzenes 10 and 11. Scheme 1Downloaded by: University of Pittsburgh. Copyrighted material.1.05 (m, 4 H, CH 2 CH 2 CH 2 CH 3 ), 1.53 [d, 18 H, 4 J H,P = 2.0 Hz, 2-/6-C(CH 3 ) 3 ], 1.84 [t, 9 H, 4 J H,P = 1.0 Hz, 4-C(CH 3 ) 3 ], 1.97 (pd, 3 H, 3 J H,P = 11.1 Hz, 1-CH 3 ), 2.34 (s, 2 H, CH 2 CH 2 CH 2 CH 3 ). 13 C{ 1 H} NMR (C 6 D 6 ): d = 11.2 (d, 1 J C,P = 41.3 Hz, 1-CH 3 ), 13.9 [s, (CH 2 ) 3 CH 3 ], 23.8 [d, J C,P = 17.9 Hz, CH 2 (CH 2 ) 2 CH 3 ], 24.1 [d, 1 J C,P = 72.5 Hz, CH 2 (CH 2 ) 2 CH 3 ], 25.7 [pt, J C,P = 1.6 Hz, CH 2 (CH 2 ) 2 CH 3 ], 35.5 [X-part of an AA¢MX spin system, 3 J C,P = 16.2, 3 J C,P = 4.9, 5 J C,P = 0.1 Hz, 2-/6-C(CH 3 ) 3 ], 36.3 [t, 3 J C,P = 12.8 Hz, 4-C(CH 3 ) 3 ], 39.0 [X-part of an AA¢MX spin system, 2 J C,P = 21.0, 2 J C,P = 3.7, 4 J C,P = 0.5 Hz, 2-/6-C(CH 3 ) 3 ], 40.7 [t, 2 J C,P = 24.7 Hz, 4-C(CH 3 ) 3 ], 110.6 (ddd, 1 J C,P = 65.9, 1 J C,P = 56.3, 3 J C,P = 3.3 Hz, C-2 and C-6), 165.8 (td, 1 J C,P = 63.3, 3 J C,P = 25.2 Hz, C-4). 31 P{ 1 H} NMR (C 6 D 6 ): d = 3.8 (t, 2 J P,P = 22.3 Hz, P-1), 229.0 (d, 2 J P,P = 22.3 Hz, P-3 and P-5). MS: m/z (%) = 372 (60, M + ), 357 (26, M + -CH 3 ), 272 (39, M + -PCt-Bu), 257 (100, M + -CH 3 -PCt-Bu), 234 (60, M + -C 10 H 18 ), 219 (14, M + -C 11 H 21 ), 169 (16, t-Bu 2 C 2 P + ). HRMS: m/z calcd for C 20 H 39 P 3 (372.50): 372.2265; found: 372.2273. Scheme 6 Downloaded by: University of Pittsburgh. Copyrighted material.CMe 2 CH 2 CH 3 ), 14.5 (d, 1 J C,P = 59.4 Hz, 1-CH 3 ), 33.0 [spin system, 2-/6-C(CH 3 ) 2 Et], 33.8 [t, 3 J C,P = 13.8 Hz, 4-C(CH 3 ) 2 Et], 38.0 (pd, 3 J C,P = 3.0 Hz, 2-/6-CMe 2 CH 2 CH 3 ), 39.4 (t, 3 J C,P = 9.7 Hz, 4-CMe 2 CH 2 CH 3 ), 43.0 [spin system, 2-/6-CMe 2 Et], 43.7 [td, 2 J C,P = 23.5, 4 J C,P = 0.3 Hz, 4-CMe 2 Et], 109.3 (ddd, 1 J C,P = 66.7, 1 J C,P = 58.3, 3 J C,P = 3.3 Hz, C-2 and C-6), 164.4 (td, 1 J C,P = 63.9, 3 J C,P = 26.0 Hz, C-4). 31 P{ 1 H} NMR (C 6 D 6 ): d = -3.7 (t, 2 J P,P = 22.3 Hz, P-1), 240.4 (d, 2 J P,P = 22.3 Hz, P-3 and P-5).

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confidence: 58%

Section: Methodsmentioning

confidence: 95%

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Organophosphorus Compounds,Part 171.1λ⁵,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphosphabenzenes

Steinbach¹,

Renner²,

Binger³

et al. 2003

Synthesis

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“…We favour a 1,4-addition as this is the known mechanism of addition of both lithium alkyls and Grignard reagents to 1. 8,9 Either proposed intermediate could rearrange via a 1,2-hydrogen migration and P-P bond formation to give 7. Although this intermediate was not observed spectroscopically, it is feasible in light of the closely related products obtained from the reaction of 1 with neutral metal hydride reagents (vide infra).…”

Section: Results and Discussion (I) Reactions With Anionic Element Te...mentioning

confidence: 99%

Reduction reactions of a 1,3,5-triphosphabenzene

Jones

Waugh

2004

Dalton Trans.

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The reactions of the triphosphabenzene, 1,3,5-P3C3But3, with LiMH4, M = Al or Ga, lead to the triphosphabicyclo[3.1.0]hexanediyl metallate complexes, [[[Li(OEt2)][MH2(P3C3But3H2)]]2], which give exo- and endo-isomers of a triphosphabicyclo[3.1.0]hexane, P3C3But3H4 upon quenching. The related reaction of [AlH3(NMe3)] with 1,3,5-P3C3But3 affords three identifiable products, viz. a triphosphabicyclo[3.1.0]hexenyl complex, [AlH2(P3C3But3H)(NMe3)], and two triphosphabicyclo[3.1.0]hexanediyl complexes, [AlH(P3C3But3H2)(NMe3)] and [Al2H4(P3C3But3H2)(NMe3)]. In contrast, the reactions of 1,3,5-P3C3But3 with either [GaH3(quin)], quin = quinuclidine, or Me3SnH lead only to the triphosphabicyclo[3.1.0]hexenyl complexes, [GaH2(P3C3But3H)(quin)] and [Me3Sn(P3C3But3H)]. Quenching of the former affords a triphosphabicyclo[3.1.0]hexene, P3C3But3H2, while quenching the latter gives its triphosphacyclohexa-1,4-diene valence isomer. Treatment of 1,3,5-P3C3But3 with "GaI" yields a GaI3 complex of the triphosphahexa-1,4-diene, [GaI3(P3C3But3H2)], whilst treatment with the anionic Ga(I) heterocycle, [:Ga[N(Ar)C(H)]2]-, Ar = C6H3Pri2-2,6, affords the known diphospholyl anion, [1,3-P2C3But3]- via a P-abstraction from the triphosphabenzene. Finally, reaction of the 1,3,5-triphosphacyclohexane, [P(OEt)C(H)(But)]3, with thionyl chloride yields the unusual lambda5, lambda5, lambda5-1,3,5-triphosphacyclohexane, [P(O)(Cl)C(H)(But)]2[P(OEt)(S)C(H)(But)]. Suggestions as to the mechanisms of a number of these reduction reactions are made and the crystal structures of seven compounds are reported.

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Beryllium & Magnesium: Organometallic ChemistryBased in part on the article Beryllium & Magnesium: Organometallic Chemistry by E. Alexander Hill which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Saulys

Hill

2005

Encyclopedia of Inorganic Chemistry

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Victor Grignard found in 1900 that solutions of organomagnesium halides form easily in the reaction of an organic halide with magnesium metal in diethyl ether. These Grignard reagents undergo useful reactions with many kinds of substrates. This discovery ushered in a new era in organometallic chemistry and provided chemists with a powerful and versatile reagent for synthesis of a wide variety of organic and organometallic compounds. This article discusses Grignard reagents in the broader context of organomagnesium chemistry. Preparatory methods surveyed include direct reaction of organic halides with the metal, exchange reactions with other organometallic compounds, as well as carbo‐ and hydrometalations. The current level of understanding of the mechanism of Grignard formation is summarized. The formation and reactivity of unusual species such as cluster Grignard reagents, for example, RMg 4 X (R = organic group, and X = halide) and polymagnesium compounds, for example, Ru[C 5 (MgCl) 5 ] 2 are also discussed. The bonding and structure of organomagnesium compounds (as well as that of beryllium analogues) as described by diffraction methods, thermochemical data, colligative properties, spectroscopic (vibrational, nuclear magnetic, and electronic) measurements, kinetic studies, mass spectrometry, and theoretical methods are outlined. The most prominent chemical property of organomagnesium compounds is their ability to deliver an effectively ‘anionic’ organic group with nucleophilic properties. As alkylating reagents, their important reactions include nucleophilic displacement of less basic leaving groups from saturated carbon atoms or other elements, addition to carbonyl groups and other unsaturated functions, and nucleophilic substitution at the acyl group of carboxylic acid derivatives. This broad array of substrates is surveyed, as are the effects of solvents and catalysts on reactivity. Less conspicuous reactions with wholly or predominantly inorganic substrates are also considered. Electron transfer reactions where organomagnesium compounds act as reductants are discussed. Organoberyllium compounds are more difficult to prepare and are less nucleophilic than their magnesium counterparts. These features, together with their high toxicity, have limited their utility. Methods of preparation, as well as descriptions of bonding, structure, and reactivity patterns are presented. Of special note are recent advances in cyclopentadienyl beryllium chemistry, as well as the advent of beryllium–silicon chemistry.

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1,4‐Addition of Grignard Reagents to 2,4,6‐Tri‐tert‐butyl‐1,3,5‐triphosphabenzene

Cited by 19 publications

References 22 publications

Organophosphorus Compounds,Part 171.1λ⁵,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphosphabenzenes

Organophosphorus Compounds,Part 171.1λ⁵,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphosphabenzenes

Reduction reactions of a 1,3,5-triphosphabenzene

Beryllium & Magnesium: Organometallic ChemistryBased in part on the article Beryllium & Magnesium: Organometallic Chemistry by E. Alexander Hill which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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1,4‐Addition of Grignard Reagents to 2,4,6‐Tri‐tert‐butyl‐1,3,5‐triphosphabenzene

Cited by 19 publications

References 22 publications

Organophosphorus Compounds,Part 171.1λ5,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphospha­benzenes

Organophosphorus Compounds,Part 171.1λ5,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphospha­benzenes

Reduction reactions of a 1,3,5-triphosphabenzene

Beryllium & Magnesium: Organometallic ChemistryBased in part on the article Beryllium & Magnesium: Organometallic Chemistry by E. Alexander Hill which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Organophosphorus Compounds,Part 171.1λ⁵,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphosphabenzenes

Organophosphorus Compounds,Part 171.1λ⁵,3,5-Triphosphabenzenes bySuccessive Addition of Lithiumalkyls and Alkyl Halides to Triphosphabenzenes