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DOI: 10.1055/s-0031-1290657
Copper-Catalyzed Cycloisomerizations of Enynols and Their Esters
Publikationsverlauf
Publikationsdatum:
05. April 2012 (online)
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Abstract
We have discovered that several platinum- or gold-catalyzed cycloisomerization reactions can also be catalyzed by copper. This Account discusses our new findings, the complementarity of copper-catalysis, and its application to the synthesis of (-)-cubebol, (-)-β-santalol, and other fragrance compounds.
1 Introduction
2 Cycloisomerization of 5-en-1-yn-3-ols: The Cyclopropanation Pathway
3 Cycloisomerization of 5-En-1-yn-3-ol-Derived Esters and Synthesis of (-)-Cubebol
4 Cycloisomerization of a 6-En-1-yn-3-ol and Its Corresponding Acetate towards the Synthesis of Thujopsanone-Like Compounds
5 Cyclization-Fragmentations of 5-En-1-yn-3-ols
6 Synthesis of (-)-β-Santalol by Cyclization-Fragmentation of a 5-En-1-yn-3-ol
7 Reactivity of 6-En-1-yn-4-ols: Cyclization-Fragmentation vs. Metathesis Reaction
8 Conclusions and Outlook
Key words
copper catalysis - cycloisomerizations - fragrances - alkynes - gold catalysis
- Recent reviews on enyne cycloisomerizations:
-
1a
Nolan SP. Acc. Chem. Res. 2011, 44: 91 -
1b
Echavarren AM.Jiménez-Nunez E. Top. Catal. 2010, 53: 924 -
1c
Fürstner A. Chem. Soc. Rev. 2009, 38: 3208 -
1d
Shen HC. Tetrahedron 2008, 64: 7847 -
1e
Jiménez-Nunez E.Echavarren AM. Chem. Rev. 2008, 108: 3326 -
1f
Michelet V.Toullec PY.Genêt J.-P. Angew. Chem. Int. Ed. 2008, 47: 4268 -
1g
Crone B.Kirsch SF. Chem. Eur. J. 2008, 14: 3514 -
1h
Fürstner A.Davies PW. Angew. Chem. Int. Ed. 2007, 46: 3410 -
1i
Jiménez-Nunez E.Echavarren AM. Chem. Commun. 2007, 333 -
1j
Gorin D.Toste JD. Nature (London) 2007, 446: 395 -
1k
Marion N.Nolan SP. Angew. Chem. Int. Ed. 2007, 46: 2750 -
1l
Marco-Contelles J.Soriano E. Chem. Eur. J. 2007, 13: 1350 -
1m
Zhang L.Sun J.Kozmin SA. Adv. Synth. Catal. 2006, 348: 2271 -
2a
Blaszykowski C.Harrak Y.Brancour C.Nakama K.Dhimane A.-L.Fensterbank L.Malacria M. Synthesis 2007, 2037 -
2b
Soriano E.Marco-Contelles J. J. Org. Chem. 2007, 72: 2651 -
2c Pt and Cu:
Barluenga J.Riesgo L.Vicente R.Lopez LA.Tomas M. J. Am. Chem. Soc. 2007, 129: 7772 -
2d
Anjum S.Marco-Contelles J. Tetrahedron 2005, 61: 4793 -
2e
Soriano E.Ballesteros P.Marco-Contelles J. Organometallics 2005, 24: 3182 -
2f
Soriano E.Marco-Contelles J. J. Org. Chem. 2005, 70: 9345 -
2g
Blaszykowski C.Harrak Y.Gonçalves M.-H.Cloarec J.-M.Dhimane A.-L.Fensterbank L.Malacria M. Org. Lett. 2004, 6: 3771 -
2h
Harrak Y.Blaszykowski C.Bernard M.Cariou K.Mainetti E.Mouriès V.Dhimane A.-L.Fensterbank L.Malacria M. J. Am. Chem. Soc. 2004, 126: 8656 -
2i
Mamane V.Gress T.Krause H.Fürstner A. J. Am. Chem. Soc. 2004, 126: 8654 -
3a
Garayalde D.Krüger K.Nevado C. Angew. Chem. Int. Ed. 2011, 50: 911 -
3b
Harrak Y.Makhlouf M.Azzaro S.Mainetti E.Romero JML.Cariou K.Gandon V.Goddard J.-P.Malacria M.Fensterbank L. J. Organomet. Chem. 2011, 696: 388 -
3c
Marion N.Lemière G.Correa A.Costabile C.Ramon RS.Moreau X.de Frémont P.Dahmane R.Hours A.Lesage D.Tabet J.-C.Goddard J.-P.Gandon V.Cavallo L.Fensterbank L.Malacria M.Nolan SP. Chem. Eur. J. 2009, 15: 3243 -
3d
Watson IDG.Ritter S.Toste FD. J. Am. Chem. Soc. 2009, 131: 2056 -
3e Au and Pt:
Moreau X.Goddard J.-P.Bernard M.Lemière G.López-Romero JM.Mainetti E.Marion N.Mouriès V.Thorimbert S.Fensterbank L.Malacria M. Adv. Synth. Catal. 2008, 350: 43 -
3f
Fürstner A.Schlecker A. Chem. Eur. J. 2008, 14: 9181 -
3g
Correa A.Marion N.Fensterbank L.Malacria M.Nolan SP.Cavallo L. Angew. Chem. Int. Ed. 2008, 47: 718 -
3h
Lemière G.Gandon V.Cariou K.Fukuyama T.Dhimane A.-L.Fensterbank L.Malacria M. Org. Lett. 2007, 9: 2207 -
3i Au and Pt:
Fürstner A.Hannen P. Chem. Eur. J. 2006, 12: 3006 -
3j
Buzas A.Gagosz F. J. Am. Chem. Soc. 2006, 128: 12614 -
3k
Cho EJ.Kim M.Lee D. Org. Lett. 2006, 8: 5413 -
3l
Johansson MJ.Gorin DJ.Staben ST.Toste FD. J. Am. Chem. Soc. 2005, 127: 18002 -
3m
Gagosz F. Org. Lett. 2005, 7: 4129 -
3n
Luzung MR.Markham JP.Toste FD. J. Am. Chem. Soc. 2004, 126: 10858 -
3o See also:
Grisé CM.Rodrigue EM.Barriault L. Tetrahedron 2008, 64: 797 -
3p For the seminal work on
the development of [(PR3)AuNTf2] catalysts,
see:
Mézailles N.Richard L.Gagosz F. Org. Lett. 2005, 7: 4133 - 4
Fehr C.Farris I.Sommer H. Org. Lett. 2006, 8: 1839 -
5a
Fehr C.Galindo J. Angew. Chem. Int. Ed. 2006, 45: 2901 -
5b
Fehr C.Winter B.Magpantay I. Chem. Eur. J. 2009, 15: 9773 - 6
Fehr C.Farris I. Angew. Chem. Int. Ed. 2006, 45: 6904 - 7
Chabardes P. Tetrahedron Lett. 1988, 29: 6253 - 8
Ohloff G.Strickler H.Willhalm B.Borer C.Hinder M. Helv. Chim. Acta 1970, 53: 623 - 9
Hatsui T.Suzuki N.Takeshita H. Chem. Lett. 1985, 639 - 10
Fehr C.Vuagnoux M.Buzas A.Arpagaus J.Sommer H. Chem. Eur. J. 2011, 17: 6214 - 11 For the preparation of [(IPr)CuNTf2] [kindly
obtained by Professor Steven P. Nolan (University of St. Andrews, St.
Andrews, UK)], see:
Fortman GC.Slawin AMZ.Nolan SP. Organometallics 2010, 29: 3966 -
12a
Luzung MR.Mauleon P.Toste FD. J. Am. Chem. Soc. 2007, 129: 12402 -
12b
Alcaide B.Almendros P.Aragoncillo C. Chem. Soc. Rev. 2010, 39: 783 - 13
Saucy G.Marbet R.Lindlar H.Isler O. Helv. Chim. Acta 1959, 42: 1945 - 14
Vedejs E.Cammers-Goodwin A. J. Org. Chem. 1994, 59: 7541 - 15
Fehr C.Vuagnoux M.Sommer H. Chem. Eur. J. 2011, 17: 3832 - 16
Bluthe N.Goré J.Malacria M. Tetrahedron 1986, 42: 1333 - 17
Shapiro ND.Toste FD. Synlett 2010, 675 - (-)-β-Santalol (very strong sandalwood odor) and (+)-β-santalol (odorless) by chiral auxiliary-based synthesis:
-
18a
Krotz A.Helmchen G. Liebigs Ann. Chem. 1994, 601 -
18b
Krotz A.Helmchen G. Tetrahedron: Asymmetry 1990, 1: 537 - (±)-β-santalol:
-
18c
Solas D.Wolinsky J. J. Org. Chem. 1983, 48: 1988 -
18d
Monti H.Corriol C.Bertrand M. Tetrahedron Lett. 1982, 23: 5539 -
18e
Sato K.Miyamoto O.Inoue S.Honda K. Chem. Lett. 1981, 1183 -
18f
Christensen PA.Willis BJ. J. Org. Chem. 1979, 44: 2012 -
18g
Kretschmar HC.Erman WF. Tetrahedron Lett. 1970, 11: 41 - 19
Fehr C, andVuagnoux M. inventors; WO 200914178. - 20
Baumann M, andHoffmann W. inventors; EP 0010213. For a long synthesis of (±)-83 (8 steps, 13% yield) of unspecified configuration and lacking spectral data, see: ; Chem. Abstr. 1980, 93, 185844 - 21
Corey EJ.Yamamoto H. J. Am. Chem. Soc. 1970, 92: 226 - 22
Fehr C.Magpantay I.Arpagaus J.Marquet X.Vuagnoux M. Angew. Chem. Int. Ed. 2009, 48: 7221 - 23
Hayashi Y.Samanta S.Gotoh H.Ishikawa H. Angew. Chem. Int. Ed. 2008, 47: 6634 - 25
Fehr C.Magpantay I.Vuagnoux M.Dupau P. Chem. Eur. J. 2011, 17: 1257 - For a related early study of Pt-catalyzed metathesis reactions leading to bridged bicyclic systems, see:
-
27a
Fürstner A.Stelzer F.Szillat H. J. Am. Chem. Soc. 2001, 123: 11863 -
27b
Fürstner A.Szillat H.Gabor B.Mynott R. J. Am. Chem. Soc. 1998, 120: 8305 - 29 Note added in proof:
Gronnier C.Kramer S.Odabachian Y.Gagosz F. J. Am. Chem. Soc. 2012, 134: 828 - For the use of Cu(I) in other types of reactions based on acetylene activation, see:
-
30a
Dudnik AS.Chernyak N.Gevorgyan V. Aldrichimica Acta 2010, 43: 37 -
30b
Schwier T.Sromek AW.Yap DML.Chernyak D.Gevorgyan V. J. Am. Chem. Soc. 2007, 129: 9868 -
30c
Montel S.Bouyssi D.Balme G. Adv. Synth. Catal. 2010, 352: 2315
References and Notes
Surprisingly, 90 and to a larger extent 91 showed a diminished ee as compared to 88 and 89, although the dr remained the same. Possibly, 90 and 91 undergo a thermal 1,2-H shift.
26Migration of the cyclopropane C-C bond opposite to the C-C=M bond in 99b (Scheme [²7] ) and 105b (Scheme [²8] ) leads to the same metathesis product. These reactions proceed via nonclassical cations, but for clarity we prefer not to draw partial bonds.
28Kindly performed by Professor M. Santelli (University of Aix-Marseille, France).