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Volumn 62, Issue 13, 2006, Pages 3103-3111

Mg-promoted reductive coupling of aromatic carbonyl compounds with trimethylsilyl chloride and bis(chlorodimethylsilyl) compounds

Author keywords

Aromatic carbonyl compounds; Electron transfer; Magnesium; Silylation

Indexed keywords

1,2 BIS(CHLORODIMETHYLSILYL)ETHANE; 1,5 DICHLOROHEXAMETHYLTRISILOXANE; ALPHA ETHOXY ALPHA TRIMETHYLSILOXY ALPHA TRIMETHYLSILOXY TOLUENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXY 2 CHLOROTOLUENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXY 2 ETHYLTHIOPHENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXY 2 METHOXYL TOLUENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXY 2 METHYLTHIOPHENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXY 3 CHLOROTOLUENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXY 4 CHLOROTOLUENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXY 4 TRIFLUORO METHYLTOLUENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXYETHYLBENZENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXYPROPYLBENZENE; ALPHA TRIMETHYLSILYL ALPHA TRIMETHYLSILOXYTOLUENE; AROMATIC COMPOUND; CARBON; CARBONYL DERIVATIVE; CHLOROSILANE; CHLOROTRIMETHYLSILANE; DIPHENYL TRIMETHYLSILYL TRIMETHYLOXYMETHANE; MAGNESIUM; N,N DIMETHYLFORMAMIDE; OXYGEN; SILANE DERIVATIVE; SILICON; SILOXANE; TOLUENE DERIVATIVE; UNCLASSIFIED DRUG;

EID: 33644663180     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2006.01.026     Document Type: Article
Times cited : (11)

References (31)
  • 17
    • 33644666106 scopus 로고    scopus 로고
    • note
    • 6
  • 19
    • 33644675614 scopus 로고    scopus 로고
    • note
    • Requirement for use of more than theoretical amount (probably 1 or 2 equiv mol) of Mg-metal may be attributed to low efficiency of electron transfer in a heterogenous reaction system between Mg-metal and starting substrate and some side-reactions such as Mg-promoted dimerization of chlorosilanes to disilanes.
  • 26
    • 33644679583 scopus 로고    scopus 로고
    • note
    • The present coupling of aromatic alkyl ketones (1h, 1i, 1q ) with bis(chlorodimethylsilyl)ethane (3 ) gave the corresponding cyclic coupling products (6h, 6i, 6q ) in similar yields, although that of 1i with TMSCl gave the corresponding product (5i ) in only 14% yield, accompanying unusual formation of 4-trimethylsilylpropiophenone (20%). This surprising phenomenon may be partially elucidated by much higher reactivity of TMSCl in comparison with bis(chlorodimethylsilyl)ethane (3 ), as shown in unusual attack of TMSCl to the p-position of reactive anion radical intermediate of 1i.
  • 27
    • 33644699155 scopus 로고    scopus 로고
    • note
    • Formation of a variety of by-products and tarric materials resulted in relatively low yield of the desired products (6 and 7 ) in Mg-promoted cyclization of aromatic ketones with dichlorosilanes (3 and 4 ).
  • 29
    • 33644673428 scopus 로고    scopus 로고
    • note
    • In this reactions, three kind of roles for TMSCl may be postulated; that is, activation of 1 as electrophiles by coordination to the oxygen atom of the carbonyl group, stabilization of anion intermediates, and activation of Mg metal.
  • 30
    • 33644695714 scopus 로고    scopus 로고
    • note
    • Ring strain of the cyclic products from the reaction of aromatic alkyl ketones (1 ) with bis(chlorodimethylsilyl) compounds (3, 4 ) may be an additional effect for their lower yield.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.