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Volumn , Issue 15, 2005, Pages 2562-2570

Synthesis and Wagner-Meerwein rearrangement of 9-(α-hydroxyalkyl) xanthenes to 10-substituted dibenz[b,f]oxepins: Scope, limitations and ab initio calculations

Author keywords

elimination; 9 hydroxyalkyl xanthene; Dehydration; Dibenz b,f oxepin; Transition state stability; Wagner Meerwein rearrangement

Indexed keywords

CATALYSIS; DEHYDRATION; NEGATIVE IONS; QUANTUM THEORY; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

EID: 26844475792     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2005-872110     Document Type: Article
Times cited : (15)

References (37)
  • 11
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    • PCT Int. Appl., WO 2003099822, 20031204, 2003
    • (a) Mercep, M.; Mesic, M.; Pesic, D. PCT Int. Appl., WO 2003099822, 20031204, 2003.
    • Mercep, M.1    Mesic, M.2    Pesic, D.3
  • 15
    • 26844570399 scopus 로고    scopus 로고
    • JP 2000044568, A20215, 2000
    • (b) Kanno, S.; Okita, T. JP 2000044568, A20215, 2000.
    • Kanno, S.1    Okita, T.2
  • 17
    • 26844580657 scopus 로고
    • Tosylate 8: Anet, F. A. L.; Bavin, P. M. G. Can. J. Chem. 1957, 35, 1081. In this work, sulfonate esters of the parent alcohols 5a-m were not investigated as starting materials for the Wagner-Meerwein rearrangement.
    • (1957) Can. J. Chem. , vol.35 , pp. 1081
    • Anet, F.A.L.1    Bavin, P.M.G.2
  • 19
    • 26844514391 scopus 로고    scopus 로고
    • Smith Kline & French patent; US 3100207, 1963
    • (a) Smith Kline & French patent; US 3100207, 1963; claims a more lengthy approach to 10-aminomethyldibenz[b,f]oxepins via 9-hydroxymethyl-9- aminoalkylxanthenes.
  • 20
    • 84982335918 scopus 로고
    • (b) Bergmann and Rabinovitz claimed the rearrangement of 9-(α-hydroxybenzyl)xanthene (5d) to 10-phenyldibenz-[b,f]oxepin but proof of structure was tentative (only IR, mp given): Bergmann, D.; Rabinovitz, M. Isr. J. Chem. 1963, 1, 125. In our hands, the substrate 5d did not rearrange, but rather gave the β-elimination product (7d, Table 1), in accordance with the theoretical calculations (vide supra, Table 3).
    • (1963) Isr. J. Chem. , vol.1 , pp. 125
    • Bergmann, D.1    Rabinovitz, M.2
  • 24
    • 0007595199 scopus 로고
    • Only one other, more cumbersome method of preparation for this aldehyde (careful DIBAL-reduction of xanthene-9-carbonyl chloride) has been reported: Rochlin, E.; Rappoport, Z. J. Am. Chem. Soc. 1992, 114, 230. In our hands, this procedure gave mostly xanthone after aqueous workup and silica gel chromatography of the crude product.
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 230
    • Rochlin, E.1    Rappoport, Z.2
  • 25
    • 26844555947 scopus 로고    scopus 로고
    • note
    • 2 (1.1 equiv), -40 °C to r.t., Huenig's base (1.2 equiv), 91% yield].
  • 26
    • 26844545234 scopus 로고    scopus 로고
    • note
    • For substrates obtained using method B, it is best to avoid workup and isolation (see ref. 12), and instead use the in situ-prepared aldehyde (4) solution (see ref. 13) directly in the next step.
  • 28
    • 26844453515 scopus 로고
    • Schrödinger, LLC: Portland, OR
    • Jaguar S. S.; Schrödinger, LLC: Portland, OR, 1991-2003.
    • (1991) Jaguar S. S.
  • 32
    • 26844507248 scopus 로고    scopus 로고
    • note
    • The putative spirocyclopropyl cyclohexadienyl transition state dates back to the pioneering work of Winstein et al., where this transition state had been invoked to rationalize rates of solvolysis and alkyl group migration in substituted, primary phenethyl tosylates and related systems; compare:


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.