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Volumn 2, Issue 5, 2010, Pages 519-522

One-Pot Synthesis of Bicyclic Fused Cyclopentenone Derivatives from 1-Ethynylcycloalkanols and Aldehydes

Author keywords

Aldehydes; C C coupling; Cyclization; Homogeneous catalysis; Ruthenium

Indexed keywords


EID: 79957459305     PISSN: 18673880     EISSN: 18673899     Source Type: Journal    
DOI: 10.1002/cctc.200900269     Document Type: Article
Times cited : (4)

References (64)
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    • See, for example.
    • See, for example.
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    • For recent examples, see.
    • For recent examples, see.
  • 17
    • 79957734007 scopus 로고    scopus 로고
    • For recent reviews on the Nazarov reaction, see.
    • For recent reviews on the Nazarov reaction, see.
  • 30
    • 79957758551 scopus 로고    scopus 로고
    • Reported examples include: a) Meyer-Schuster and Rupe-type rearrangements to afford α,β-unsaturated carbonyl compounds; b) C-C couplings of tertiary alkynols with enolizable ketones to generate conjugated dienones or diene-diones; c) furan, pyran, or pyrrole ring- formation reactions by cyclizative coupling of secondary propargylic alcohols with 1,3-dicarbonyl compounds and primary amines. See.
    • Reported examples include: a) Meyer-Schuster and Rupe-type rearrangements to afford α, β-unsaturated carbonyl compounds; b) C-C couplings of tertiary alkynols with enolizable ketones to generate conjugated dienones or diene-diones; c) furan, pyran, or pyrrole ring- formation reactions by cyclizative coupling of secondary propargylic alcohols with 1, 3-dicarbonyl compounds and primary amines. See.
  • 38
    • 79957704836 scopus 로고    scopus 로고
    • Nazarov-type cyclizations by coupling of enolizable vinyl ketones and aldehydes have been described. See, for example.
    • Nazarov-type cyclizations by coupling of enolizable vinyl ketones and aldehydes have been described. See, for example.
  • 41
    • 79957679702 scopus 로고    scopus 로고
    • To our knowledge, the involvement of propargylic alcohols in intermolecular one-pot Nazarov-type processes is unprecedented. Only two-step intermolecular cyclopentannulation reactions, by coupling of cycloalkanones and acyclic propargylic alcohols, have been described. They involve the initial addition of the dilithium salt of the alkynol to the carbonyl compound and a subsequent acid-catalyzed Rupe/Nazarov sequence. See, for example.
    • To our knowledge, the involvement of propargylic alcohols in intermolecular one-pot Nazarov-type processes is unprecedented. Only two-step intermolecular cyclopentannulation reactions, by coupling of cycloalkanones and acyclic propargylic alcohols, have been described. They involve the initial addition of the dilithium salt of the alkynol to the carbonyl compound and a subsequent acid-catalyzed Rupe/Nazarov sequence. See, for example.
  • 44
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    • Some multistep intramolecular examples are also known. See, for example.
    • T. Hiyama, M. Shinoda, H. Saimoto, H. Nozaki, Bull. Chem. Soc. Jpn. 1981, 54, 2747-2758. Some multistep intramolecular examples are also known. See, for example.
    • (1981) Bull. Chem. Soc. Jpn. , vol.54 , pp. 2747-2758
    • Hiyama, T.1    Shinoda, M.2    Saimoto, H.3    Nozaki, H.4
  • 48
    • 79957680954 scopus 로고    scopus 로고
    • In the absence of the precatalyst 1, cyclopentenone 3a is formed in only 15% yield after 24 h at 75°C;
    • In the absence of the precatalyst 1, cyclopentenone 3a is formed in only 15% yield after 24 h at 75°C;
  • 49
    • 79957727994 scopus 로고    scopus 로고
    • The coupling of the independently synthesized enone 1-acetylcyclooctene with benzaldehyde has also been studied. In the absence of TFA, complex 1 by itself (5 mol%) was not able to promote the formation of 3a, even after 24 h at 75°C. Under the same reaction conditions, the use of TFA (50 mol%) in the absence of complex 1 led to 3a in only 29% GC yield after 24 h. In contrast, the combined use of 1 (5 mol%) and TFA (50 mol%) afforded 3a in high yield (93% by GC) after 10 h of heating. These results clearly indicate the active role of the Lewis acid-ruthenium species in the reaction sequence.
    • The coupling of the independently synthesized enone 1-acetylcyclooctene with benzaldehyde has also been studied. In the absence of TFA, complex 1 by itself (5 mol%) was not able to promote the formation of 3a, even after 24 h at 75°C. Under the same reaction conditions, the use of TFA (50 mol%) in the absence of complex 1 led to 3a in only 29% GC yield after 24 h. In contrast, the combined use of 1 (5 mol%) and TFA (50 mol%) afforded 3a in high yield (93% by GC) after 10 h of heating. These results clearly indicate the active role of the Lewis acid-ruthenium species in the reaction sequence.
  • 50
    • 79957692583 scopus 로고    scopus 로고
    • The preparation of compounds 3a and 3l through alternative routes has been described.
    • The preparation of compounds 3a and 3l through alternative routes has been described.
  • 53
    • 79957744913 scopus 로고    scopus 로고
    • The intermediate formation of 4 was confirmed by monitoring the catalytic reaction by GC/MS;
    • The intermediate formation of 4 was confirmed by monitoring the catalytic reaction by GC/MS;
  • 54
    • 0000894377 scopus 로고
    • Rupe-type rearrangements proceed through the initial dehydration of the propargylic alcohol, followed by hydration of the C≡C bond of the resulting enyne. For a review on the Rupe reaction, see
    • Rupe-type rearrangements proceed through the initial dehydration of the propargylic alcohol, followed by hydration of the C≡C bond of the resulting enyne. For a review on the Rupe reaction, see: S. Swaminathan, K. V. Narayanan, Chem. Rev. 1971, 71, 429-438.
    • (1971) Chem. Rev. , vol.71 , pp. 429-438
    • Swaminathan, S.1    Narayanan, K.V.2
  • 55
    • 79957669800 scopus 로고    scopus 로고
    • Metal-catalyzed addition of carboxylic acids to terminal alkynes is a well-known process, with ruthenium catalysts playing a prominent role. For reviews, see.
    • Metal-catalyzed addition of carboxylic acids to terminal alkynes is a well-known process, with ruthenium catalysts playing a prominent role. For reviews, see.
  • 57
    • 20444478248 scopus 로고    scopus 로고
    • in (Ed.: S.-I. Murahashi), Wiley-VCH, Weinheim, For specific examples of ruthenium-catalyzed Markovnikov addition of carboxylic acids to 1,3-enynes, see.
    • C. Fischmeister, C. Bruneau, P. H. Dixneuf in Ruthenium in Organic Synthesis (Ed.: S.-I. Murahashi), Wiley-VCH, Weinheim, 2004, pp. 189-217. For specific examples of ruthenium-catalyzed Markovnikov addition of carboxylic acids to 1, 3-enynes, see.
    • (2004) Ruthenium in Organic Synthesis , pp. 189-217
    • Fischmeister, C.1    Bruneau, C.2    Dixneuf, P.H.3
  • 60
    • 79957786265 scopus 로고    scopus 로고
    • In the absence of directing functional groups, the generation of fused cyclopentenone rings through Nazarov-type processes usually proceeds without control of the ring-fusion stereochemistry. See, for example.
    • In the absence of directing functional groups, the generation of fused cyclopentenone rings through Nazarov-type processes usually proceeds without control of the ring-fusion stereochemistry. See, for example.
  • 64
    • 79957671048 scopus 로고    scopus 로고
    • Formation of 8b and 9b through an acid- or metal-catalyzed isomerization of the C=C bond in 8a and 9a has been ruled out. Isolated compounds 8a and 9a remained unchanged when treated with 1/TFA for 24 h at 75°C.
    • Formation of 8b and 9b through an acid- or metal-catalyzed isomerization of the C=C bond in 8a and 9a has been ruled out. Isolated compounds 8a and 9a remained unchanged when treated with 1/TFA for 24 h at 75°C.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.