Palladium-mediated transannular cyclizations of medium-ring olefinic enolsilanes

Tetrahedron Letters

Volumn 46, Issue 47, 2005, Pages 8149-8152

  Kende, Andrew S ^a   Nelson, Clara E Mota ^b   Fuchs, Sébastien ^a  

^a UNIVERSITY OF ROCHESTER   (United States)

^b PPG INDUSTRIES   (United States)

Author keywords

Bicyclic ketones lactones; Cyclization; Medium ring enolsilanes; Palladium(II) mediated cycloalkenylation

Indexed keywords

ALKENE DERIVATIVE; PALLADIUM; SILANE DERIVATIVE;

ARTICLE; CHEMICAL BOND; CYCLIZATION; ELIMINATION REACTION;

EID: 27144534243     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2005.09.125     Document Type: Article

References (39)

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22. Silylations of the macrolactones were carried out with HMPA (1.1 equiv) instead of DMPU. The lithium enolate was trapped with TBDMSCl (1.1 equiv) and slowly warmed to room temperature. After chromatography, the very unstable ketene acetals 5 and 6 were used immediately in the palladium(II) reactions.
23. Cyclizations were typically carried out by addition of a solution of silyl enol ether in acetonitrile/dichloromethane, to a solution of palladium acetate (1.0 equiv) in acetonitrile. After stirring for 16 h under argon at room temperature, the black solution was evaporated to dryness under reduced pressure, diluted with hexanes, and filtered through a plug of Florisil. The filtrate was concentrated, and the resulting yellow oil purified by chromatography (silica gel, gradient hexanes 100%-hexanes-ethyl acetate 9:1).
24. 13C NMR, and MS) of cyclization product 14 were identical to those from an authentic sample obtained during the preparation of the substrate 2.
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34. + = 138 (9%), 121, 110, 91, 80, 79 (100%), 68, 53, 41.
35. + = 152, 124, 109, 95, 83, 81, 69, 68, 67.
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39. The compound 23 was obtained in two steps from 24, first by generating the kinetic enolate of 24 with LDA (1.2 equiv) in dry THF and trapping with TMSCl (1.2 equiv), and then by the same oxidative degradation used to transform 22 to 23, with an overall yield of 39%.