β-tributylstannylacrylates. Stereospecific synthesis conjugate additon of tributylstaknylcopper

Seitz, David E.; Lee, Shi-Hung

doi:10.1016/s0040-4039(01)92379-2

Cited by 47 publications

(2 citation statements)

References 13 publications

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“…Nevertheless, when these reactions were carried out with lithium phenylthio(trimethylstannyl)cuprate instead of Me 3 SnLi, the yield of substitution products was substantially increased . Stannyl cuprates also react with β-X-α,β-unsaturated esters (X = Cl, I, OTos, OTf, SPh) , as well as with vinyl iodides and vinyl triflates to give vinylstannanes in good to excellent yields. All of these reactions may be considered either as nucleophilic substitutions or addition−elimination reactions.…”

Section: Introductionmentioning

confidence: 99%

Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an S_RN1 Vinylic Mechanism

2004

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Ketones are converted into vinyl diethyl phosphate esters (VinDEP), which under photostimulation reacted with sodium trimethylstannide (1) or sodium triphenylstannide (2) in liquid ammonia affording vinylstannanes via a vinylic S(RN)1 mechanism. Thus, (1-phenylvinyl)DEP (3), (3,4-dihydro-1-naphthyl)DEP (7), (3,4-dihydro-2-naphthyl)DEP (9), (E)-(1,2-diphenylvinyl)DEP (12), (E/Z)-(1-methyl-2-phenylvinyl)DEP (14) and (E)-(1-phenyl-2-methylvinyl)DEP (16) react with 1 and 2, under photostimulation, leading to the corresponding substitution products in good to excellent yields (45-89%). On the other hand, there is no reaction between (1-cyclohexenyl)DEP (5) or (1-benzylvinyl)DEP (18) with either 1 or 2, under similar conditions. These reactions appear to be strongly dependent on structural features of the vinyl phosphate since only conjugated vinyl phosphates afforded substitution products. These substitution reactions are completely regioselective and stereoconvergent. It seems to be the first example of a vinylic S(RN)1 process involving organotin anions as nucleophiles.

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Section: Introductionmentioning

confidence: 99%

Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an S_RN1 Vinylic Mechanism

2004

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“…Substitution methods for the preparation of vinylstannanes include the use of PhS(Me3Sn)CuLi with a number of /3-iodo-a,/3-unsaturated cyclic ketones15 and Bu3SnCu with /3-halo or -tosyl acrylates. 16 Presumably these reactions involve an addition elimination process. In each case the stannyl group is placed in the position from which the leaving group departed.…”

Section: Introductionmentioning

confidence: 99%

Protodestannylation of carbomethoxy-substituted vinylstannanes: Kinetics, stereochemistry and mechanisms

Cochran¹,

Williams²,

Bronk³

et al. 1989

Organometallics

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Five carbomethoxy-and four carboethoxy-substituted vinylstannanes have been prepared. Methyl 2-(trimethylstannyl)acrylate and ethyl 2-(trimethylstannyl)acrylate were prepared by hydrostannation of methyl and ethyl propiolate under polar conditions. The former compound was also prepared by Pd(0) catalyzed hydrostannation of methyl propiolate. The E and Z isomers of methyl and ethyl 3-(trimethylstannyl)acrylate were prepared by free radical hydrostannation of methyl and ethyl propiolate. Methyl and ethyl 2-(trimethylstannyl)fumarate were synthesized by hydrostannation of dimethyl and diethyl acetylenedicarboxylate under polar conditions. Methyl 2-(trimethylstannyl)maleate was prepared by Pd(0)-catalyzed hydrostannation of dimethyl acetylenedicarboxylate. Structures were confirmed by and 13C NMR. The stereochemistry of stannyl cleavage was determined by deuteriodestannylation and XH NMR of the products. The methyl 3-(trimethylstannyl)acrylate isomers gave retention of configuration while the methyl 2-(trimethylstannyl)fumarate and -maleate resulted in approximately equal ratios of isomeric deuteriodestannylation products. In this latter case an allenol intermediate is proposed. Second-order rate constants for protodestannylation, in methanol-5 % water, were determined at three temperatures for the carbomethoxy compounds. Activation parameters were calculated from the rate data. The carbomethoxy group was found to be deactivating for all compounds except methyl 2-(trimethylstannyl)maleate. In this case, interaction of the syn carbomethoxy groups may serve to provide a more reactive route to the allenol intermediate.

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Benzyl 3-(Tributylstannyl)acrylate

Piers

Rogers

2001

Encyclopedia of Reagents for Organic Synthesis

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β-tributylstannylacrylates. Stereospecific synthesis conjugate additon of tributylstaknylcopper

Cited by 47 publications

References 13 publications

Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an S_RN1 Vinylic Mechanism

Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an S_RN1 Vinylic Mechanism

Protodestannylation of carbomethoxy-substituted vinylstannanes: Kinetics, stereochemistry and mechanisms

Benzyl 3-(Tributylstannyl)acrylate

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β-tributylstannylacrylates. Stereospecific synthesis conjugate additon of tributylstaknylcopper

Cited by 47 publications

References 13 publications

Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an SRN1 Vinylic Mechanism

Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an SRN1 Vinylic Mechanism

Protodestannylation of carbomethoxy-substituted vinylstannanes: Kinetics, stereochemistry and mechanisms

Benzyl 3-(Tributylstannyl)acrylate

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Product

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Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an S_RN1 Vinylic Mechanism

Photostimulated Reactions of Vinyl Phosphate Esters with Triorganostannides. Evidence for an S_RN1 Vinylic Mechanism