Alkyl- And Acyl-Substituted Vinylstannanes: Synthesis and Reactivity in Electrophilic Substitution Reactions

Cochran, John C.; Prindle, Vicki; Young, Heather A.; Kumar, Mark H.; Tom, Samson; Petraco, Nicholas; Mohoro, Clare; Kelley, Brendan J.

doi:10.1081/sim-120005609

Cited by 5 publications

(5 citation statements)

References 43 publications

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“…The reaction with Bu 3 SnH provided a 82:18 mixture of α- and β-( E )-isomers whereas the use of Me 3 SnH furnishes exclusively the α-isomer (Scheme ). Although the reaction with Me 3 SnD is also regioselective, it is not stereoselective and provides a 1:1 mixture of α-( Z ) and α-( E )-isomers . Of note is the chemical fragility of α-tributylstannyl conjugated enones during purification, leading to protodestannylation products.…”

Section: Scope and Limitationsmentioning

confidence: 86%

“…Although the reaction with Me3SnD is also regioselective, it is not stereoselective and provides a 1:1 mixture of -(Z) and -(E)-isomers. 69 Of note is the chemical fragility of -tributylstannyl conjugated enones during purification, leading to protodestannylation products. It is best to use such products without delay following the hydrostannation step.…”

Section: Scheme 31 Pd-catalyzed Hydrostannation Of Unconjugated Diynesmentioning

confidence: 99%

“…Conjugated alkynones 23,68 also exhibit good to excellent regioselectivity for the formation of the α-isomer, but the level of selectivity seems to depend on the nature of the tin hydride employed (E)-isomers. 69 Of note is the chemical fragility of αtributylstannyl conjugated enones during purification, leading to protodestannylation products. It is best to use such products without delay following the hydrostannation step.…”

Section: 1 1 2 a R O M A T I C A L K Y N E Smentioning

confidence: 99%

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Hydrostannation of Alkynes

2019

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In this review, we present an overview of hydrostannation of alkynes until the end of 2018. Mechanism of the tin hydride addition on a triple bond is discussed at the beginning of this review in the presence of metal catalysts as Pd, Ru-based complexes, Lewis acids and under radical conditions. Then, stereoselectivity as well as regioselectivity aspects of tin hydride addition on the carbon triple bond is discussed using metal-catalysis, radical conditions or Lewis acids. In each of these items, the reactions will be studied for terminal alkynes and then, for internal alkynes. Applications of hydrostannation of alkynes using metal-catalysis is presented in a variety of total syntheses with Pd, Mo, Rh and Ru-complexes to provide highly functionalized vinyl stannanes derivatives as key-intermediates. Comparison with other methods providing vinyl stannanes using metallostannation followed by protonation is presented before the last section dealing with a summary of classical experimental conditions used to achieve the hydrostannation of alkynes.

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Section: Scope and Limitationsmentioning

confidence: 86%

Section: Scheme 31 Pd-catalyzed Hydrostannation Of Unconjugated Diynesmentioning

confidence: 99%

Section: 1 1 2 a R O M A T I C A L K Y N E Smentioning

confidence: 99%

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Hydrostannation of Alkynes

2019

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“…It should be mentioned that although these radical additions led in most cases to mixtures of trineophyltin adducts, we were able to separate and purify these by column chromatography. This suggests that trineophyltin adducts are more stable than their trimethyl- and tributyltin analogues, which have been reported to decompose during chromatographic purification 2 or to isomerize …”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of Stannyl Enones via Palladium-Catalyzed and Free Radical Hydrostannation of Alkynyl Ketones with Trineophyltin Hydride

et al. 2003

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A study on the addition of trineophyltin hydride (1) to alkynones under free radical (AIBN and Et3B) and palladium-catalyzed [(PPh3)2PdCl2] conditions is reported. The results obtained indicate that the addition of 1 to eight ynones catalyzed by bis(triphenylphosphine)palladium(II) chloride led in all cases to addition products in very high yields (80-96%). These additions take place with excellent regio- and stereochemistry, leading to the alpha adducts as major products in seven out of the eight cases studied. Also the E adducts, resulting from a syn attack, were the only (seven cases) or the predominant (one case) products. The radical hydrostannations initiated by AIBN of ynones 2-5 with 1 led to addition products in good yields (60-88%); with the more hindered ketones 6 and 7-9 the yields obtained were lower. The radical additions initiated by triethylboron to ynones 2-6 follow a similar pattern but with lower yields; no addition products in the hydrostannation of ynones 7-9 were detected. The new acyl-substituted vinylstannanes, owing to their greater stability compared with that of their tributyl- and trimethylstannyl analogues, can be purified by column chromatography using neutral alumina (in all cases) or silica gel 60 (in most cases) as adsorbents. Full 1H, 13C, and 119Sn NMR data are given.

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“…The synthesis of (Z)-iodovinyl pyrone 11 from readily available (Z)-3-iodo-2-methyl propenal (16) 9 proceeded analogously (Scheme 2). Addition of the dianion, followed To complete the synthesis of the simple molluscan polypropionates, three vinyl stannanes 19, 10 20, and 21 11 were readily prepared according to well-established procedures (Scheme 3). With both iodovinyl pyrones and vinyl stannanes in hand, we explored their cross-coupling using a variety of Stille-coupling conditions.…”

mentioning

confidence: 99%