Organometallic alkenes: The first stable silene in the neopentyl series

Delpon‐Lacaze, G.; Couret, C.

doi:10.1016/0022-328x(94)87133-7

Cited by 34 publications

(18 citation statements)

References 10 publications

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“…Therefore, a iiew highly selective method for the generation of 2 was developed. Starting from dichlorodiphenylsilane diphenyldivinylsilane ( 5 ) was prepared by Grignard reaction. [221 In a one-pot procedure 5 was then treated with triflic acid to give (CF,SO,),SiVi, and refunctionalized with HNEt,CI to yield an 82 O h yield of purc 2 after distillation (Scheme 2).…”

Section: Synthesis Of Dichlorodivinylsilane (2)mentioning

confidence: 99%

Towards 2‐Silaallenes: Synthesis of Spirocyclic Precursors

Goetze¹,

Herrschaft²,

Auner³

1997

Chemistry A European J

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Section: Synthesis Of Dichlorodivinylsilane (2)mentioning

confidence: 99%

Towards 2‐Silaallenes: Synthesis of Spirocyclic Precursors

Goetze¹,

Herrschaft²,

Auner³

1997

Chemistry A European J

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“…Until recently no silene of this series has been stabilized at room temperature in a monomeric form; these derivatives dimerize spontaneously by a head-to-tail fashion to 1,3disilacyclobutanes ( R=Me, R'=Ph [1]; R=CI, R'= CH=CH2 [2]; R=Me, R"= Cp(CO)2Fe [3]; R=CI, R'=Ph [4]; R=CI, R'=R"2N [5]; R=Me, R = CH=CH2 [6] ).Dimesitylneopentylsilene Mes2Si=CH-CH2-tBu of which we have recently described the synthesis and the characterization, is until now the sole stable silene in the neopentyl series [7], In order to try to obtain such a silene of a sufficient lifetime, we have used one mesityl and one methyl group at the silicon atom.…”

Section: Introductionmentioning

confidence: 99%

Methylmesitylneopentylsilene: Synthesis and Study of Its Dimerization

Delpon‐Lacaze¹,

Couret²,

Veith³

et al. 1995

Main Group Metal Chemistry

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Methylmesitylneopentylsilene Me(Mes)Si=CHCH2tBu 1 is prepared as reactive intermediate by the reaction of methyl(mesityl)vinylfluorosilane 2 with tBuLi. It can be evidenced by trapping reactions with tBuLi (excess) or 2,3-dimethylbutadiene. Without trapping agent, the molecules dimerize to form 4 different isomers of 1,3-disilacyclobutanes 4 (a-d). The Z/Z isomer 4d is the major dimer (83%). Its crystal structure is reported. The influence of the ratio for E-l to Z-l (93/7) on the stereochemical distribution of dimers is discussed.

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“…Silenes with comparable substitution patterns are unknown, but similarly structured derivatives, such as (E)-(Me 3 Si)TipSiϭC(OSiMe 3 )Ad (δ 29 Si ϭ 40.3; Ad ϭ 1-adamantyl), [14] Mes 2 SiϭCHCH 2 tBu (δ 29 Si ϭ 77.6) [4] or (Me 3 Si)(tBuMe 2 Si)SiϭAdЈ (δ 29 Si ϭ 51.7, AdЈ ϭ 2-adamantylidene) [6] also show characteristic downfield shifts of the SiϭC signals in their 29 Si NMR spectra. Similarly, 1c and 2-tert-butyl-4,5,6-trimethylphenyllithium (1:2) gave the silene 9c (Scheme 1).…”

Section: Reaction Of (Dichloromethyl)methylbis(trimethylsilyl)silane mentioning

confidence: 99%

“…[1] In numerous reactions transient silenes occur as reactive intermediates, but until now the number of synthetic methods affording stable, isolable silenes is rather limited. [3] Elimination of lithium chloride after addition of tert-butyllithium to the carbonϪcarbon double bond of chloro(vinyl)silanes is also the crucial step in establishing SiϭC bonds in a method developed by the groups of Jones and Auner, which was successfully used by Couret et al in 1994 in the preparation of the stable 1,1-dimesityl-481 of 1b with 2,4,6-triisopropylphenyllithium (molar ratio 1:2). [2] In 1983 Wiberg and his group succeeded in applying the classical 1,2 salt elimination to the synthesis of the stable silene Me 2 SiϭC(SiMetBu 2 )SiMe 3 and provided the results of its X-ray analysis.…”

Section: Introductionmentioning

confidence: 99%

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Reaction of the (Dichloromethyl)oligosilanes R(Me3Si)2Si−CHCl2 (R = Me, Ph, Me3Si) with Organolithium Reagents and the Synthesis of Novel Kinetically Stabilized Silenes

Schmohl¹,

Reinke²,

Oehme³

2001

Eur. J. Inorg. Chem.

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The dichloromethyloligosilanes R1(Me3Si)2Si−CHCl2 (1a,b) (1a: R1 = Me; 1b: R1 = Ph), prepared by treatment of methylbis(trimethylsilyl)silane or phenylbis(trimethylsilyl)silane respectively, with chloroform and potassium tert‐butoxide, treated with the organolithium reagents R2Li (R2 = Me, Ph) to produce the intermediate organolithium derivatives R1R22Si−CLi(SiMe3)2 (10). Hydrolysis of 10 during the aqueous workup afforded the [bis(trimethylsilyl)methyl]silanes R1R22Si−CH(SiMe3)2 (2); quenching of the reaction mixture with chlorotrimethylsilane gave the [tris(trimethylsilyl)methyl]silanes R1R22Si−C(SiMe3)3 (11). The formation of 10 is discussed as proceeding through a remarkable series of isomerization processes involving the transient silenes R1R2Si=C(SiMe3)2 (7), which in the presence of an effective excess of R2Li are immediately trapped to give 10. By the use of sterically congested organolithium derivatives, the nucleophilic addition of R2Li to the Si=C bond of 7 can be prevented and kinetically stabilized silenes obtained. Thus, Ph(2,4,6‐iPr3C6H2)Si=C(SiMe3)2 (8b) was synthesized by the reaction of 1b with 2,4,6‐triisopropylphenyllithium (molar ratio 1:2). Similarly, (Me3Si)(2,4,6‐iPr3C6H2)Si=C(SiMe3)2 (8c) and (Me3Si)(2‐tBu‐4,5,6‐Me3C6H)Si=C(SiMe3)2 (9c) were prepared from (dichloromethyl)tris(trimethylsilyl)silane (1c) and 2,4,6‐triisopropylphenyllithium or 1c and 2‐tert‐butyl‐4,5,6‐trimethylphenyllithium (1:2), respectively, but due to difficulties in the separation of starting material and side products, 8b, 8c, and 9c were obtained in impure form only. Despite the steric congestion, the compounds are reactive and exhibit the usual behavior of silenes. Thus 8b, 8c, and 9c were chemically characterized by the reaction with water to give silanols, by the addition of methanol to give methoxysilanes and by formal [2+2] cycloadditions with benzaldehyde to afford stable 1,2‐oxasiletanes. 1‐Methyl‐1‐(2,4,6‐triisopropylphenyl)‐2,2‐bis(trimethylsilyl)silene (8a), produced as intermediate from 1a and 2,4,6‐triisopropylphenyllithium (1:2), proved to be unstable in the presence of excess aryllithium compound. Thus, only the addition product Me(2,4,6‐iPr3C6H2)2SiCH(SiMe3)2 (14) was isolated (after hydrolysis).

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Organometallic alkenes: The first stable silene in the neopentyl series

Cited by 34 publications

References 10 publications

Towards 2‐Silaallenes: Synthesis of Spirocyclic Precursors

Towards 2‐Silaallenes: Synthesis of Spirocyclic Precursors

Methylmesitylneopentylsilene: Synthesis and Study of Its Dimerization

Reaction of the (Dichloromethyl)oligosilanes R(Me3Si)2Si−CHCl2 (R = Me, Ph, Me3Si) with Organolithium Reagents and the Synthesis of Novel Kinetically Stabilized Silenes

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