RSS-Feed abonnieren
DOI: 10.1055/s-0031-1289752
Straightforward Synthesis of Nonconjugated Cyclohex-3-enone and Conjugated 4-Methylenecyclohex-2-enone Derivatives
Publikationsverlauf
Publikationsdatum:
27. März 2012 (online)
![](https://www.thieme-connect.de/media/synthesis/201209/lookinside/thumbnails/10.1055-s-0031-1289752-1.jpg)
Abstract
The synthesis of nonconjugated cyclohex-3-enones via the regiodivergent cobalt-catalysed Diels-Alder reactions of 2-(trimethylsilyloxy)buta-1,3-diene with alkynes and hydrolysis of the dihydroaromatic intermediates is described. The application of bidentate phosphine ligands versus pyridine-imine ligands led to the regioselective formation of one out of the two possible regioisomeric products when terminal or unsymmetrically substituted alkynes were applied. The cyclohex-3-enone products were isolated mostly in good yields without isomerisation of the carbon-carbon double bond into conjugation based on the mild reaction conditions. The use of acetoxymethyl-substituted alkynes led to the conjugated 4-methylenecyclohex-2-enones after deprotection of the silyl enol ether.
Key words
alkynes - catalysis - cobalt - Diels-Alder reaction - dienes - nonconjugation
-
1a
Stapleford KSJ. Synth. Commun. 1982, 12: 651 -
1b
Crowshaw K.Newstead RC.Rogers NAJ. Tetrahedron Lett. 1964, 2307 -
2a
Irie H.Katakawa J.Mizuno Y.Udaka S.Taga T.Osaki K. J. Chem. Soc., Chem. Commun. 1978, 717 -
2b
Nemoto H.Hashimoto M.Kurobe H.Fukumoto K. J. Chem. Soc., Perkin Trans. 1 1985, 927 -
2c
Rickards RW.Rodwell JL.Schmalzl KJ. J. Chem. Soc., Chem. Commun. 1977, 849 -
2d
Wild H. J. Org. Chem. 1994, 59: 2748 -
2e
Wild H.Born L. Angew. Chem., Int. Ed. Engl. 1991, 30: 1685 ; Angew. Chem. 1991, 103, 1729 -
2f
Katsuta Y.Aoyama Y.Osone H.Wada A.Ito M.
J. Chem. Soc., Perkin Trans. 1 1997, 1405 -
3a
McAndrew BA. J. Chem. Soc., Perkin Trans. 1 1979, 1837 -
3b
Balme G.Goré J. J. Org. Chem. 1983, 48: 3336 -
3c
Birch AJ. J. Proc. R. Soc. N.S.W. 1949, 83: 245 -
3d
Jung ME.Rayle HL. Synth. Commun. 1994, 24: 197 -
3e
Chamakh A.Amri H. Tetrahedron Lett. 1998, 39: 375 -
4a
Kim JN.Im YJ.Kim JM. Tetrahedron Lett. 2002, 43: 6597 -
4b
Park DY.Kim SJ.Kim TH.Kim JN. Tetrahedron Lett. 2006, 47: 6315 -
5a
Danz M.Hilt G. Adv. Synth. Catal. 2011, 353: 303 -
5b
Auvinet A.-L.Harrity JPA.Hilt G. J. Org. Chem. 2010, 75: 3893 -
5c
Hilt G.Janikowski J. Org. Lett. 2009, 11: 773 -
5d
Hilt G.Danz M. Synthesis 2008, 2257 -
5e
Mörschel P.Janikowski J.Hilt G.Frenking G. J. Am. Chem. Soc. 2008, 130: 8952 -
5f
Hilt G.Janikowski J.Hess W. Angew. Chem. Int. Ed. 2006, 45: 5204 ; Angew. Chem. 2006, 118, 5328 -
5g
Hilt G.Paul A.Harms K.
J. Org. Chem. 2008, 73: 5187 -
5h
Hilt G.Paul A.Hengst C. Synthesis 2009, 3305 -
5i
Hilt G.Hess W.Harms K. Synthesis 2008, 75 -
5j
Treutwein J.Hilt G. Angew. Chem. Int. Ed. 2008, 47: 6811 ; Angew. Chem. 2008, 120, 6916 -
5k
Hilt G.Janikowski J. Angew. Chem. Int. Ed. 2008, 47: 5243 ; Angew. Chem. 2008, 120, 5321 - For recent reviews concerning cobalt-catalysed reactions involving cyclopentadienylcobalt-type catalyst systems, see:
-
5l
Leboeuf D.Gandon V.Malacria M. In Handbook of Cyclization Reactions Vol. 1:Ma S. Wiley-VCH; Weinheim: 2009. p.367 -
5m
Galan BR.Rovis T. Angew. Chem. Int. Ed. 2009, 48: 2830 -
5n
Omae I. Appl. Organomet. Chem. 2008, 22: 149 -
5o
Hess W.Treutwein J.Hilt G. Synthesis 2008, 3537 -
5p
Omae I. Appl. Organomet. Chem. 2007, 21: 318 -
5q
Kotha S.Brahmachary E.Lahiri K. Eur. J. Org. Chem. 2005, 4741 -
5r
Malacria M.Aubert C.Renaud J.-L. In Science of Synthesis, Houben-Weyl Methods of Molecular Transformations Vol. 1:Lautens M. Georg Thieme Verlag; Stuttgart: 2001. p.439 -
5s
Saito S.Yamamoto Y. Chem. Rev. 2000, 100: 2901 - 8
Hilt G.Smolko KI.Lotsch BV. Synlett 2002, 1081 - 10
Jung ME.Rayle HL. Synth. Commun. 1994, 24: 197 - 11
Thomas MT.Fallis AG. J. Am. Chem. Soc. 1976, 98: 1227
References
Ligands: dppe = 1,2-bis(diphenylphosphino)ethane; py-imine = 2,4,6-trimethyl-N-(pyridin-2-ylmethylene)aniline.
7In previous reactions the use of iron powder increased the chemo- and regioselectivity. In this series of experiments, the iron powder additive was not necessary and was therefore not added.
9The catalysts with phosphine-type ligands show reactivity for the Diels-Alder reaction as well as for 1,4-hydrovinyl-ation. In contrast, catalysts with pyridine-imine-type ligands are unreactive in 1,4-hydrovinylation reactions thus far.