RSS-Feed abonnieren
DOI: 10.1055/s-2002-35622
New Preparation of sp2 Organometallic Derivatives
Publikationsverlauf
Publikationsdatum:
20. November 2002 (online)
![](https://www.thieme-connect.de/media/synthesis/200217/lookinside/thumbnails/10.1055-s-2002-35622-1.jpg)
Abstract
Various polysubstituted, metalated olefins are easily prepared from heterosubstituted alkenes such as vinyl enol ethers, vinyl sulfides, sulfoxides and even sulfones in a one-step procedure. A complete isomerization was observed in this process, which leads only to the E isomer.
-
1 Introduction
-
1.1 Oxidative Metallation of Organic Halides
-
1.2 Metal-Halogen Exchange
-
1.3 Metal-Hydrogen Exchange
-
1.4 Hydrometallation Reactions
-
1.5 Carbometallation Reactions
-
1.6 Transmetallation Reactions
-
1.7 The Shapiro Reaction
-
2 Limitations of these Methods
-
3 Zirconocene Complexes in Organic Synthesis
-
4 Discussion
-
4.1 Vinylic Enol Ether into Vinylic Organometallic Derivatives
-
4.1.1 Mechanistic Discussion
-
4.2 Vinylic Thioenol Ether into Vinylic Organometallic Derivatives
-
4.3 Vinyl Sulfoxides into Vinylic Organometallic Derivatives
-
4.4 Vinyl Sulfones into Vinylic Organometallic Derivatives
-
5 Conclusions
Key words
sp2 organometallics - vinyl sulfides - vinyl sulfones - vinyl enol ethers - vinyl sulfoxides - zirconocene complexes - stereoselectivity
-
1a
Wakefield BJ. In Organomagnesium Methods in Organic Synthesis Academic Press; New York: 1995. -
1b
Wakefield BJ. In The Chemistry of Organolithium Compounds Pergamon Press; New York: 1974. -
1c
Wakefield BJ. In Organolithiums Methods Pergamon Press; New York: 1988. -
1d
Schlosser M. In Organometallics in Synthesis - A Manual 2nd Ed.: John Wiley & Sons Ltd; New York: 2002. - 2
Bailey WF.Patricia JJ. J. Organomet. Chem. 1988, 352: 1 - 3
Boudier A.Bromm LO.Lotz M.Knochel P. Angew. Chem. Int. Ed. 2000, 39: 4414 - 4
Kitagawa K.Inoue A.Shinokubo H.Oshima K. Angew. Chem. Int. Ed. 2000, 39: 2481 - 5
Snieckus V. Chem. Rev. 1990, 90: 879 - 6
Brown HC.Kramer GW.Levy AB.Midland MM. Organic Synthesis via Boranes Wiley-Interscience; New York: 1975. - 7
Zweifel G.Miller JA. Organic Reactions 1984, 32: 375 - 8
Wipf P.Jahn H. Tetrahedron 1996, 52: 12853 - 9
Zweifel G.Steele RB. J. Am. Chem. Soc. 1967, 89: 5185 -
10a
Marek I. J. Chem. Soc., Perkin Trans 1 1999, 535 -
10b
Marek I.Normant JF. In Metal-Catalyzed Cross-Coupling ReactionsDiederich F.Stang PJ. Wiley-VCH; Weinheim: 1988. p.271 - 11
Normant JF.Alexakis A. Synthesis 1981, 841 - 12
Negishi E.Kondakov DY.Choueiry D.Kasai T.Takahashi T. J. Am. Chem. Soc. 1996, 118: 9577 - 13
Heck RF. J. Am. Chem. Soc. 1968, 90: 5518 - 14
Kocienski P. In Organic Synthesis via OrganometallicsEnders D.Gais HJ.Klein E. Vieweg; Wiesbaden: 1993. p.203 - 15
Alexakis A.Marek I.Mangeney P.Normant JF. Tetrahedron 1991, 47: 1677 - 16
Chamberlin AR.Bloom SH. Org. React. 1990, 39: 1 - 17
Marek I. Titanium and Zirconium in Organic Synthesis Wiley-VCH; Weinheim: 2002. -
18a
Ito H.Taguchi T.Hanzawa Y. Tetrahedron Lett. 1992, 33: 1295 -
18b
Hanzawa Y.Kiyono H.Tanaka N.Taguchi T. Tetrahedron Lett. 1997, 38: 4615 -
19a
Ito H.Nakamura T.Taguchi T.Hanzawa Y. Tetrahedron Lett. 1992, 33: 3769 -
19b
Ito H.Motoki Y.Taguchi T.Hanzawa Y. J. Am. Chem. Soc. 1993, 115: 8835 -
19c
Ito H.Ikeuchi Y.Taguchi T.Hanzawa Y.Shiro M. J. Am. Chem. Soc. 1994, 116: 5469 -
19d
Hanzawa Y.Kiyono H.Tanaka N.Taguchi T. Tetrahedron Lett. 1997, 38: 4615 - 20
Ito H.Taguchi T.Hanzawa Y. Tetrahedron Lett. 1992, 33: 7873 -
21a
Ito H.Taguchi T. Tetrahedron Lett. 1997, 38: 5829 -
21b
Sato A.Ito H.Taguchi T. J. Org. Chem. 2000, 65: 918 -
21c
Ito H.Kuroi H.Ding H.Taguchi T. J. Am. Chem. Soc. 1998, 120: 6623 -
21d
Ito H.Sato A.Taguchi T. Tetrahedron Lett. 1999, 40: 3217 -
22a
Hanzawa Y.Ito H.Taguchi T. Synlett 1995, 29 -
22b
Ito H.Nakamura T.Taguchi T.Hanzawa Y. Tetrahedron 1995, 51: 4507 - 23
Ito H.Taguchi T.Hanzawa Y. J. Org. Chem. 1993, 58: 774 - 24
Takahashi T.Kotora M.Fischer R.Nishihara Y.Nakajima K. J. Am. Chem. Soc. 1995, 117: 11039 -
25a
Ichikawa J.Fujiwara M.Nawata H.Okauchi T.Minami T. Tetrahedron Lett. 1996, 37: 8799 -
25b
Fujiwara M.Ichikawa J.Okauchi T.Minami T. Tetrahedron Lett. 1999, 40: 7261 - 26
Alexakis A.Normant JF. Isr. J. Chem. 1984, 24: 113 -
27a
Negishi E.Van Horn DE. J. Am. Chem. Soc. 1977, 99: 3168 -
27b
Okukado N.Van Horn DE.Klima WL.Negishi E. Tetrahedron Lett. 1978, 1027 -
27c
Negishi E.Okukado N.King AO.Van Horn DE.Spiegel BJ. Am. Chem. Soc. 1978, 100: 2254 - 28
Ganchegui B.Bertus P.Szymoniak J. Synlett 2001, 123 - 29
Negishi E.Takahashi T. Bull. Chem. Soc. Jpn. 1998, 71: 755 - 30
Takahashi T.Fujimoto T.Seki T.Saburi M.Uchida Y.Rousset CJ.Negishi E. J. Chem. Soc., Chem. Commun. 1990, 182 - 31
Negishi E.Choueiry D.Nguyen TB.Swanson DR.Suzuki N.Takahashi T. J. Am. Chem. Soc. 1994, 116: 9751 -
32a
Mintz EA.Ward AS.Tice DS. Organometallics 1985, 4: 1308 -
32b
Ward AS.Mintz EA.Kramer MP. Organometallics 1988, 7: 8 -
33a
Erker G.Rosenfeldt F. Tetrahedron Lett. 1981, 22: 1379 -
33b
Erker G.Rosenfeldt F. Tetrahedron 1982, 38: 1285 -
34a
Cohen T.Doubleday MD. J. Org. Chem. 1990, 55: 4784 -
34b
Cohen T.Bhupathy M. Acc. Chem. Res. 1989, 22: 152 -
35a
Foubelo F.Gutierrez A.Yus M. Tetrahedron Lett. 1999, 40: 8173 -
35b
Yus M. Chem. Soc. Rev. 1996, 155 -
36a
Marek I. Chem. Rev. 2000, 100: 2887 -
36b
Marek I.Normant JF. Chem. Rev. 1996, 96: 3241 - 37
Patai S.Rappoport Z.Stirling CJM. The Chemistry of Sulphones and Sulphoxides Wiley; Chichester: 1988. - 38
Howard WA.Parkin G. J. Am. Chem. Soc. 1994, 116: 606 -
39a
Cuvigny T.Herve du Penhoat C.Julia M. Tetrahedron Lett. 1983, 24: 4311 -
39b
Julia M.Lauron H.Stacino J.-P.Verpeaux J.-N.Jeannin Y.Dromzee Y. Tetrahedron 1986, 42: 2475 -
40a
Guijarro D.Yus M. Tetrahedron Lett. 1994, 35: 2965 -
40b
Najera C.Yus M. Tetrahedron 1999, 55: 10547 -
40c
Simpkins NS. Sulphones in Organic Synthesis Pergamon Press; New York: 1993. - 41
Cuvigny T.Herve du Penhoat C.Julia M. Tetrahedron Lett. 1983, 24: 4311 -
42a
Fabre J.-L.Julia M.Verpeaux J.-N. Bull. Soc. Chim. Fr. 1985, 762 -
42b
Fabre J.-L.Julia M.Verpeaux J.-N. Bull. Soc. Chim. Fr. 1985, 772 -
42c
Baldwin JE.Adlington RM.Ichikawa Y.Kneale CJ. J. Chem. Soc., Chem. Commun. 1988, 702 -
43a
Trost BM. Bull. Chem. Soc. Jpn. 1988, 61: 107 -
43b
Backvall J.-E.Chinchilla R.Najera C.Yus M. Chem. Rev. 1998, 98: 2291 -
44a
Creary X. J. Org. Chem. 1985, 50: 5080 -
44b
Stang PJ.Hanack M.Subramanian LR. Synthesis 1982, 85 -
45a
Takahashi T.Suzuki N.Kageyama M.Nitto Y.Saburi M.Negishi E. Chem. Lett. 1991, 1579 -
45b
Takahashi T.Nitto Y.Seki T.Saburi M.Negishi E. Chem. Lett. 1990, 2259 -
45c
Takahashi T.Li Y. Titanium and Zirconium in Organic SynthesisMarek I. Wiley-VCH; Weinheim: 2002. p.50 - 46
Farhat S.Marek I. Angew. Chem. Int. Ed. 2002, 41: 1410 - 47
Liard A.Marek I. J. Org. Chem. 2000, 65: 7218