Cycloisomerization of aromatic homo and bis-homopropargylic alcohols via catalytic ru vinylidenes: Formation of benzofurans and isochromenes

Organic Letters

Volumn 11, Issue 22, 2009, Pages 5350-5353

  Várela Fernández, Alejandro ^a   González Rodríguez, Carlos ^a   Varela, Jesús A ^a   Castedo, Luis ^a   Saá, Carlos ^a  

^a UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 70749085501     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol902212h     Document Type: Article

References (44)

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18. 2 has been previously used in stoichiometric reactions with homo- and bis-homopropargylic alcohols to give stable cyclic oxacarbene Ru complexes: Bruce, M. I.; Swincer, A. G.; Thomson, B. J.; Wallis, R. C Aust. J. Chem. 1980, 33, 2605.
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23. For reviews of Ru-vinylidenes, see ref 2. For books, see: (a) Murahashi, S.-I., Ed. Ruthenium in Organic Synthesis; Wiley-VCH: Weinheim, 2004.
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25. 3) were used for cycloisomerization of bis-homopropargyl alcohols. See ref 5.
26. Other Ru(II) catalysts and amines failed or gave lower yields. See the Supporting Information for details.
27. The same result was obtained without catalyst by heating in pyridine: Kanazawa, C.; Terada, M. Tetrahedron Lett. 2007, 48, 933.
28. Yield comparable to the one obtained using other Ru catalytic conditions (64%) and using Rh catalysts (61%). See refs 5 and 6 for more details.
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34. The 5-endo is probably preferred on the basis of the driving force of forming a new aromatic furan ring when the phenolic OH reacts.
35. To the best of our knowledge, only Ru-catalyzed oxidative cyclization of homopropargylic alcohols to y-butyrolactones has been described. See refs 4 and 5.
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38. On the other hand, the aliphatic homopropargylic alcohol 1,1diphenylbut-3-yn-l-ol could be cycloisomerized to 2,2-diphenyl-2, 3dihydrofuran in 30% yield. See the Supporting Information for details.
39. This type of alkyne dimerization has been observed before; see: Bassetti, M.; Pasquini, C.; Raneri, A.; Rosato, D. J. Org. Chem. 2007, 72, 4558.
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43. The deuteration experiment was performed with a 3:7 mixture of deuterated alkyne (shown in Scheme 2) and deuterated alcohol (not shown). See the Supporting Information for details.
44. Initial results with aromatic alkynyl amines and amides are promising (C-N bond formation) and will be the subject of future reports.