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Volumn 44, Issue 30, 2005, Pages 4753-4757

[2+1] Cycloadditions of terminal alkynes to norbornene derivatives catalyzed by palladium complexes with phosphinous acid ligands

Author keywords

Alkynes; Cycloaddition; Cyclopropanes; Palladium; Phosphane ligands

Indexed keywords

ADDITION REACTIONS; CATALYSIS; DERIVATIVES; ORGANIC ACIDS; PALLADIUM;

EID: 23044489277     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200500879     Document Type: Article
Times cited : (129)

References (71)
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    • With enantiopure L1, the complex 1 was clearly identified by NMR spectroscopy. The acetato-bridged structure was supported by the ESI mass spectrum of the palladium complex 1 (see Supporting Information).
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    • Cycloadduct 3a was also contaminated with 5% of an unidentified byproduct.
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    • 3 (dba = dibenzylideneacetone) did not promote the reaction at all.
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    • 3CN (6% yield).
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    • The catalytic system was stable under the experimental conditions described and could be recovered after the reaction by column chromatography.
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    • A difference in reactivity was observed by using trimethylsilylacetylene in place of propargylsilane 3c: Only an adduct of hydroalkynylation was obtained as a single diastereomer in 68% yield.
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    • see reference [21a]
    • 2π mechanism, which is a symmetry-forbidden reaction. They have therefore been generally interpreted to occur by cleavage to a diradical followed by rapid intramolecular trapping of the diradical by the π bond (see reference [21a]).
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    • The same reaction carried out with cyclopentene in place of norbornene derivatives did not work. No oligomers or self-coupling adducts of the phenylethyne 3a have been observed.
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    • 2-coordinated alkyne intermediate A. The first involves a direct 1,2-hydrogen migration over the carbon triple bond. In contrast, the second mechanism occurs through a 1,3-shift of the hydride to the alkynyl ligand after oxidative addition of the C-H bond to Pd.
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    • note
    • sp2-H at δ = 6.55 ppm (see Supporting Information).
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    • See Supporting Information for full synthetic details and characterization of new compounds. CCDC 265344-265346 (4i, 6i, and 5) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.