Mild procedure for the catalytic bis(stannylation) of alkynes with hexaalkylditins

Organic Letters

Volumn 5, Issue 10, 2003, Pages 1653-1655

  Mancuso, John ^a   Lautens, Mark ^a  

^a UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; AMINE; CARBAMIC ACID DERIVATIVE; ETHER DERIVATIVE; ISONITRILE DERIVATIVE; PALLADIUM; SILANE DERIVATIVE; TIN DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0141741274     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034284e     Document Type: Article

References (31)

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20. 119Sn NMR analysis indicated formation of only the (Z)-bis(stannyl)alkene.
21. If the silica is not properly deactivated, small amounts of monostannylated products are generated and are difficult to separate from the bis(stannylated) product.
22. Proto- and iodo-destannylation occurs preferentially at the terminal stannyl group; see refs 5a and 5f, respectively.
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28. Our proposed catalytic cycle is similar to that of Piers and Skerlj; see ref 5c.
29. Alternatively, passage through a palladium(IV) intermediate via an oxidative process cannot be ruled out.
30. We have observed that terminal 1-ene-6-ynes will, in addition to generating the expected bis(stannylated) product, cyclize in a 5-exo-trig fashion to yield minor amounts (<30%) of bis(stannylated) exo-methyl-enecyclopentane products. This provides further evidence concerning the regioselectivity of the stannylpalladative step.
31. 3P, which generates an underligated, electron-rich palladium complex, failed for this reaction, giving only trace amounts of product.