Retention of configuration in nucleophilic vinylic halide substitution. II. Stereospecific preparation of vinylarsines

Aguiar, Adam M.; Archibald, Thomas

doi:10.1021/jo01283a062

Cited by 31 publications

(11 citation statements)

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“…For general background to and applications of diphenylarsino derivatives, see: Hill et al (1983); Song et al (2005). For the preparation of the title compound, see: Aguiar & Archibald (1967); Burfield et al (1977Burfield et al ( , 1978; Tzschach & Lange (1962). For closely related structures, see: Hill et al (2001); Shawkataly et al (2005).…”

Section: Related Literaturementioning

confidence: 99%

“…Solvents were dried by recommended literature routes (Burfield et al, 1977(Burfield et al, , 1978 and the title compound was prepared by the reaction of diphenylarsino lithium with 1,6-dibromohexane in dry THF at 273 K under nitrogen atmosphere (Aguiar et al, 1967;Tzschach & Lange, 1962). Colourless plates of suitable quality for single crystal X-ray diffraction studies were obtained by slow evaporation from ethanol solution.…”

Section: S2 Experimentalmentioning

confidence: 99%

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1,6-Bis(diphenylarsino)hexane

Shawkataly¹,

Khan²,

Goh³

et al. 2009

Acta Cryst E

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The title diphenylarsino compound, C30H32As2 or Ph2As(CH2)6AsPh2, lies about a crystallographic inversion centre located at the mid-point of the central Csp 3—Csp 3 bond of the methylene chain. The two benzene rings bonded to As are inclined to one another at a dihedral angle of 75.98 (8)°. In the crystal structure, weak intermolecular C—H⋯π interactions stack the molecules down the b axis.

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Section: Related Literaturementioning

confidence: 99%

Section: S2 Experimentalmentioning

confidence: 99%

1,6-Bis(diphenylarsino)hexane

Shawkataly¹,

Khan²,

Goh³

et al. 2009

Acta Cryst E

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“…Reagents: i, Ph2PLi; ii, H20/H202; iii, -LiBr to form diarylacetylenes on reaction with organolithium reagentsZ3 and the reaction is thought to involve initial metallation to give compound (27) followed by aryl migration. Carbene involvement has been discounted in these reactions on the grounds that no addition to added alkenes could be observed ; 24 reaction of 1,l -dibromo-2,2-diphenylethylene with lithium diphenylphosphide in the presence of cyclohexene offered evidence (g.c.-mass spectrum) of only traces of the adduct (30).…”

Section: LImentioning

confidence: 99%

Phosphides and arsenides as metal–halogen exchange reagents. Part 1. Dehalogenation of aliphatic dihalides

Gillespie¹,

Walker²

1983

J. Chem. Soc., Perkin Trans. 1

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Lithium diphenylphosphide and arsenide have been investigated as reagents for metal-halogen exchange. Reactions involving two molar equivalents of the anions with 1,2-dibromoethylenes lead to moderate to good yields of acetylenes and smaller yields of phosphorus-containing by-products. Similar reactions with 2,3-dichlorobuta-l,3-diene and 2-chlorobuta-l,3-diene give SN2' rather than direct substitution products. Evidence is presented that adamantene is an initial product in the reaction of lithium diphenylphosphide with 1,Z-di-iodo-and 1,2-dibromo-adarnantane, but not with 1,2-dichIoroadamantane, although 1 -and 2-adamantyldiphenylphosphine oxides are formed in every case. Finally reactions of phosphide anion with geminal dihalides were briefly investigated ; 1 ,I -dibromo-2,2-diphenylethylene gave diphenylacetylene as the major product.Attack on halogen by neutral tervalent phosphorus has been commonly observed and through the work of Appe12 and Castro has been developed into a series of general synthetic procedures. These compounds have also been used as debrominating reagent^.^ By comparison there have been few reports of attack on halogen by phosphide anions and we are aware of only one example of dehalogenation, that of 1,2-dibromoethane to give ethylene.6 However, we were encouraged to investigate group 5 anions as metallating, and hence dehalogenat ing, reagents since organometallic compounds, especially organolithium, have been extensively used in this way' and the greater polarisability of group 5 nucleophiles suggests that attack on halogen would be more likely in these cases than for carbon nucleophiles.Our choice of lithium compounds as reagents was on the basis of greatest polarisability and this is supported by the preferential attack on halogen by lithium phosphides and carbon by sodium phosphides.6 On the same basis the larger arsenide anion should be a more satisfactory reagent than phosphide. Results and Discussion(a) Reactions of 1,2-Dihalogenoa1kenes.-Aguiar and his co-workers have extensively investigated the reactions of vicinal vinyl dichlorides with phosphides * and have shown that nucleophilic displacement at carbon is the predominant pathway; t however, the softer halogen should encourage attack on bromine in the corresponding dibromide.The addition of two molar equivalents of lithium diphenylphosphide or lithium diphenylarsenide to 1 ,Zdibromoethylene (la) (64 : 36, cis : trans), a$-dibromostyrene (lb) (29 : 71, cis : trans), and a,P-dibromostilbene (lc) (40 : 60, cis : trans) in refluxing tetrahydrofuran gave in each case the corresponding acetylene ( Table 1). Determination of any preferred stereochemistry for the elimination was precluded by the rapid isomerisation of the dibromides under the reaction condit i o n~.~ In the phosphide reactions, after oxidative work-up, diphenylphosphinic acid was also formed, while small yields of the oxides (2), (3), and (4) were isolated from reactions with the dibromides (la), (lb), and (lc), respectively.The formation of acetylenes in these react...

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“…Die Umsetzungen erfolgen gewohnlich in siedendem:Dioxan-oder THF, seltener in Monoglyme und besonders vorteilhaft in fliissigem NH,. Nach vorangegangener Beseitigung von M R 3 durch Zugabe eines Aquivalents NH,CI [28], NH,Br [lS], [29] oder tert-Butylchlorid [30] ist die sofortige weitere Nutzung der Arsidlosung im Sinne einer Eintopfreaktionmoglich. Im Falle spezieller Reaktionspartner kann dieser Schritt unterbleiben [31], [32].…”

Section: Spaltungsreaktwnen An Tertiiiren Arsinenunclassified

Synthese und Reaktionsverhalten As‐substituierter Alkaliarside

Tzschach

Voigtländer

1979

Zeitschrift fuer Chemie

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Retention of configuration in nucleophilic vinylic halide substitution. II. Stereospecific preparation of vinylarsines

Cited by 31 publications

References 0 publications

1,6-Bis(diphenylarsino)hexane

1,6-Bis(diphenylarsino)hexane

Phosphides and arsenides as metal–halogen exchange reagents. Part 1. Dehalogenation of aliphatic dihalides

Synthese und Reaktionsverhalten As‐substituierter Alkaliarside

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