.alpha.,.alpha.' Dianions of aliphatic ketones and the 1,3,5 trianion of 2,4-pentanedione: strongly nucleophilic carbonyl synthons

Hubbard, James S.; Harris, Thomas M.

doi:10.1021/ja00526a069

Cited by 39 publications

(6 citation statements)

References 3 publications

(4 reference statements)

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“…1,1-Diphenylacetone-derived dianion 6 , prepared by treatment of 1,1-diphenylacetone successively with 1 molar equiv each of KH and n -BuLi in THF, reacted readily with diorganodichlorosilanes (Ph 2 SiCl 2 , Me 2 SiCl 2 , Et 2 SiCl 2 , MeSiHCl 2 ) at 0 °C in THF to give solid products in 40−70% yield. The use of higher reaction temperatures decreased the product yield, but lower reaction temperatures did not result in an increase in product yield.…”

Section: Resultsmentioning

confidence: 99%

“…Preparation of 1,1-Diphenylacetone Dianion [Ph 2 CC(O)CH 2 ] 2 - , 6. 1,1-Diphenylacetone dianion was prepared according to a literature procedure 4a. A 100 mL round-bottomed Schlenk flask equipped with a magnetic stir bar and a rubber septum was charged with 0.5 g (12.5 mmol) of KH and 50 mL of THF.…”

Section: Methodsmentioning

confidence: 99%

“…After the resulting orange solution had been stirred at room temperature for 40 min, it was cooled to 0 °C and 4.93 mL of 2.53 M n -BuLi (12.5 mmol) in hexane was added. The resulting red suspension was stirred at 0 °C for 5−7 min 4a…”

Section: Methodsmentioning

confidence: 99%

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Reactions of the 1,1-Diphenylacetone-Derived Dianion as a C,O-Dinucleophile with Organohalosilanes and -germanes

Seyferth¹,

Wang²,

Langer³

et al. 1997

Organometallics

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1,1-Diphenylacetone dianion reacts with diorganodichlorosilanes to give 1,1,5,5-tetraorgano-3,7-bis(diphenylmethylene)-1,5-disila-2,8-dioxacyclooctanes, while 1,1-diphenylacetone dianion reacts with diorganodifluorosilanes to give a positional isomer, 1,1,5,5-tetraorgano-3,7-bis(diphenylmethylene)-1,5-disila-2,6-dioxacyclooctane. The structures of 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene)-1,5-disila-2,8-dioxyacyclooctane and 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene)-1,5-disila-2,6-dioxacyclooctane were determined by X-ray crystallography. A 10-membered cyclic compound and a 6-membered cyclic compound also were prepared by the reaction of 1,1-diphenylacetone dianion with 1,2-dichlorotetramethyldisilane and 1,3-dichlorohexamethyltrisilane, respectively. The structure of 1,1,2,2,6,6,7,7-octamethyl-4,9-bis(diphenylmethylene)-1,2,6,7-tetrasila-3,10-dioxacyclodecane was determined by X-ray crystallography. 1,1-Diphenylacetone dianion reacts with diphenyldichlorogermane and diphenyldifluorogermane to give 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene)-1,5-digerma-2,6-dioxacyclooctane. The structure of 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene)-1,5-digerma-2,6-dioxacyclooctane was determined by X-ray crystallography. A possible explanation for the difference in the reactions observed with Ph2SiCl2 and Ph2SiF2 is presented. Experiments involving reactions of the 1,1-diphenylacetone dianion with monochlorosilanes indicate that a Si−CH2, not an Si−O, bond is formed first.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Reactions of the 1,1-Diphenylacetone-Derived Dianion as a C,O-Dinucleophile with Organohalosilanes and -germanes

Seyferth¹,

Wang²,

Langer³

et al. 1997

Organometallics

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“…4a The diketoester 3 was synthesized from 2,4-pentanedione (1). After bis-allylation of 1 (NaH, s-BuLi, TMEDA, allylbromide, cyclohexane), 9 compound 2 was obtained in 34% yield (Scheme 2). Treatment of 2 with NaH, followed by addition of ethyl bromoacetate furnished an inseparable mixture of the desired monoalkylated compound 3 and the dialkylated product 3¢.…”

Section: Figurementioning

confidence: 99%

Desymmetrization of Substituted 1,3-Diketones: A Formal Synthesis of (+)-Stemoamide

Bogliotti¹,

Dalko²,

Cossy³

2006

Synlett

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“…A complex possibly involved a monoanion enolate of acetone/LHMDS/HMDS/THF. By comparison to LHMDS (hexamethyldisilazine, p K a ∼26), LDA (from diisopropylamine, p K a ∼35) is a strong enough base for the preparation of β-diketone dianions but not the acetone dianion, which was prepared and reported by Harris by treatment of this simple ketone with two different bases and assisted with tetramethyletylenediamine (TMEDA) …”

Section: Introductionmentioning

confidence: 99%

Preparation of a Select Tautomer of Various Unsymmetrical 1,3,5-Pentanetriones, (1Z,4Z)-1-(Aryl)-1,5-dihydroxy-5-phenylpenta-1,4-dien-3-ones, a 4H-1-benzothiopyran-4-one, and a 2-(2-oxoyl)quinolin-4(1H)-one

Mabe

Knick

Shuler

et al. 2015

Ind. Eng. Chem. Res.

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Deprotonation of 1-benzoylacetone with excess lithium hexamethyldisilazide (LHMDS) or lithium diisopropylamide (LDA) resulted in a dilithium dianion-type intermediate, which underwent a Claisen-type condensation with substituted aromatic esters or an isatoic anhydride to afford unsymmetrical 1,3,5-pentanetriones or a cyclized heterocyclic product when the C-acylated intermediates contained a select ortho-substituted phenacyl pendant group. Spectral data indicated that a particular tautomer, a (1Z,4Z)-1-(4-aryl)-1,5-dihydroxy-5-phenylpenta-1,4-dien-3-one, resulted upon recrystallization of the linear products. Condensation−cyclization of the dianion-type intermediate with methyl thiosalicylate resulted in a phenacyl benzoheterocyclic thiopyranone and with 5-chloroisatoic anhydride in a phenacyl quinolinone. X-ray crystal analysis of several products afforded additional proof of structure, especially regarding which tautomer was isolated.

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.alpha.,.alpha.' Dianions of aliphatic ketones and the 1,3,5 trianion of 2,4-pentanedione: strongly nucleophilic carbonyl synthons

Cited by 39 publications

References 3 publications

Reactions of the 1,1-Diphenylacetone-Derived Dianion as a C,O-Dinucleophile with Organohalosilanes and -germanes

Reactions of the 1,1-Diphenylacetone-Derived Dianion as a C,O-Dinucleophile with Organohalosilanes and -germanes

Desymmetrization of Substituted 1,3-Diketones: A Formal Synthesis of (+)-Stemoamide

Preparation of a Select Tautomer of Various Unsymmetrical 1,3,5-Pentanetriones, (1Z,4Z)-1-(Aryl)-1,5-dihydroxy-5-phenylpenta-1,4-dien-3-ones, a 4H-1-benzothiopyran-4-one, and a 2-(2-oxoyl)quinolin-4(1H)-one

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