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Volumn 63, Issue 43, 2007, Pages 10646-10656

Palladium(II)- and mercury(II)-catalyzed rearrangements of propargyl acetates

Author keywords

[No Author keywords available]

Indexed keywords

5,6 BICYCLIC 1,4 CYCLOPENTADIENYL ACETATE; ACETIC ACID; ACETIC ACID DERIVATIVE; ALKENYL GROUP; ALKYNYL GROUP; CYCLOPENTENONE DERIVATIVE; MERCURY; PALLADIUM; PROPARGYL ACETATE DERIVATIVE; UNCLASSIFIED DRUG;

EID: 34548479742     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2007.08.008     Document Type: Article
Times cited : (32)

References (47)
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    • For other examples of Au-mediated rearrangements of propargylic/homopropargylic esters, see:
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    • note
    • TLC evidence indicated that some ketone 8a was formed during the course of the reaction. Rautenstrauch also observed this phenomenon in the absence of AcOH and suggested that it occurred via formal loss of ketene.
  • 28
    • 34548499265 scopus 로고    scopus 로고
    • note
    • 2 was optimal.
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    • 1H NMR shows similar peaks to that of a structurally-related 2-ethoxycyclopentadiene:
    • 1H NMR shows similar peaks to that of a structurally-related 2-ethoxycyclopentadiene:. Hatanaka M., Himeda Y., Imashiro R., Tanaka Y., and Ueda I. J. Org. Chem. 59 (1994) 111
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    • note
    • Longer reaction times or higher catalyst loadings led to complex mixtures minus starting material. Crude NMR indicated that some cyclized product was likely formed, but it could not be isolated free of other compounds.
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    • Classes of palladium(II) complexes examined: Pd(II)-bisoxazolines (trifluoroacetate and tetrafluoroborate derivatives); see:
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    • and Pd(II)-BINAP (tetrafluoroborate derivative). In most experiments, no cyclization was observed. Instead, the reaction produced a mixture of uncyclized products. Pd(II) chloride-bisoxazoline complex did promote the rearrangement of 7a, but isolated product 8a was racemic
    • Kato K., Tanaka M., Yamamoto Y., and Akita H. Tetrahedron Lett. 43 (2002) 1511 and Pd(II)-BINAP (tetrafluoroborate derivative). In most experiments, no cyclization was observed. Instead, the reaction produced a mixture of uncyclized products. Pd(II) chloride-bisoxazoline complex did promote the rearrangement of 7a, but isolated product 8a was racemic
    • (2002) Tetrahedron Lett. , vol.43 , pp. 1511
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    • note
    • A reviewer correctly pointed out that intermediate 20 could cyclize to give 23. This can also be viewed as a 4π-electrocyclization if a (zwitterionic) resonance form of the carbene is considered.
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    • note
    • 1H NMR spectra from reactions with terminal alkyne substrates revealed the presence of related compounds in trace amounts.
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    • For mechanistic work concerning [1,5] H shifts in cyclopentadienes, see:
    • For mechanistic work concerning [1,5] H shifts in cyclopentadienes, see:. McLean S., and Haynes P. Tetrahedron 21 (1965) 2329
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    • For a recent example of asymmetric mercuriocyclization of γ-hydroxy-cis-alkenes, see:
    • For a recent example of asymmetric mercuriocyclization of γ-hydroxy-cis-alkenes, see:. Kang S.H., and Kim M. J. Am. Chem. Soc. 125 (2003) 4684
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    • note
    • 1H NMR J values for each diastereomer indicate a trans-relationship between the cyclopentenone stereocenters.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.