RSS-Feed abonnieren
DOI: 10.1055/s-2004-815936
A Cross Metathesis Based Protocol for the Effective Synthesis of Functionalised Allyl Bromides and Chlorides
Publikationsverlauf
Publikationsdatum:
26. Januar 2004 (online)
![](https://www.thieme-connect.de/media/synthesis/200403/lookinside/thumbnails/10.1055-s-2004-815936-1.jpg)
Abstract
Functionalised allyl halides, useful starting materials for the preparation of substituted organometallic reagents can be simply obtained by a straightforward approach. Hoveyda’s ruthenium carbene catalyst 3, used in catalytic amount (2 mol%), is able to promote the cross metathesis of allyl bromide and chloride with a variety of different substituted olefins giving the corresponding functionalised allyl halides in satisfactory yields. trans-Olefins are obtained as major diastereoisomers reaching 90:10 (trans:cis) ratio when allyl chloride is used as the metathesis partner. This reaction represents a simple and accessible way for the preparation of valuable precursors for functionalised organometallic reagents. In particular, the use of functionalised allyl bromides (10b and 13) in the enantioselective Nozaki-Hiyama reaction promoted by [Cr(Salen)Cl] is presented.
Key words
allyl halides - cross metathesis - ruthenium catalyst - functionalised olefins
-
1a
Schwab P.France MB.Ziller JW.Grubbs RH. Angew. Chem., Int. Ed. Engl. 1995, 34: 2039 -
1b
Schwab P.Ziller JW.Grubbs RH. J. Am. Chem. Soc. 1996, 118: 100 -
2a
Schrock RR.Murdzek LS.Bazan GC.Robbins J.DiMare M.O’Regan M. J. Am. Chem. Soc. 1990, 112: 3875 -
2b
Fu GC.Grubbs RH. J. Am. Chem. Soc. 1992, 114: 7324 -
3a
Scholl M.Ding S.Lee CW.Grubbs RH. Org. Lett. 1999, 1: 953 -
3b
Chatterjee AK.Grubbs RH. Org. Lett. 1999, 1: 1751 -
3c
Chatterjee AK.Morgan JP.Scholl M.Grubbs RH. J. Am. Chem. Soc. 2000, 122: 3783 - 4
Garber SB.Kingsbury JS.Gray BL.Hoveyda AH. J. Am. Chem. Soc. 2000, 122: 8168 - 5
Brümmer O.Rückert A.Blechert S. Chem.-Eur. J. 1997, 3: 441 - 6
Grela K.Bieniek M. Tetrahedron Lett. 2001, 42: 6425 - 7
Langer P.Holtz E. Synlett 2001, 110 - 8
Engelhart FC.Schmitt MJ.Taylor RE. Org. Lett. 2001, 3: 2209 - 9
Imhof S.Randl S.Blechert S. Chem. Commun. 2001, 1692 -
10a
Gessler S.Randl S.Blechert S. Tetrahedron Lett. 2000, 41: 9973 -
10b
Rivard M.Blechert S. Eur. J. Org. Chem. 2003, 2225 -
11a
Choi T.-L.Chatterjee AK.Grubbs RH. Angew. Chem. Int. Ed. 2001, 40: 1277 -
11b
Cossy J.BouzBouz S.Hoveyda AH. J. Organomet. Chem. 2001, 634: 216 - 12
Blechert S.Connon SJ. Angew. Chem. Int. Ed. 2003, 42: 1900 - 13
Bandini M.Cozzi PG.Umani-Ronchi A. Chem. Commun. 2002, 919 ; and references therein -
14a
Trnka TM.Day MW.Grubbs RH. Angew. Chem. Int. Ed. 2001, 40: 3441 ; and references therein -
14b
Goldberg SD.Grubbs RH. Angew. Chem. Int. Ed. 2002, 41: 807 - 15
Blanco OM.Castedo L. Synlett 1999, 557 - 16
Liu B.Das SK.Roy R. Org. Lett. 2002, 4: 2723 - 17
Elemes Y.Foote CS. J. Am. Chem. Soc. 1992, 114: 6044 - 18
Van der Schaaf PA.Kolly R.Kirner H.-J.Rime F.Mühlebach A.Hafner A. J. Organomet. Chem. 2000, 606: 65 - 19 The use of trans-1,3-dibromo or trans-1,3-dichloropropene does not improve the yield causing instead the failure of the reaction. For this strategy see:
Blackwell HE.O’Leary DJ.Chatterjee AK.Washenfelder RA.Bussmann DA.Grubbs RH. J. Am. Chem. Soc. 2000, 122: 5871 - Selected examples:
-
20a [Sn]:
Marshall JA. In Organometallic in Synthesis: A ManualSchlosser M. Wiley; Chichester: 2002. p.353 -
20b [Ti]:
Reetz MT. In Organometallic in Synthesis: A ManualSchlosser M. Wiley; Chichester: 2002. p.817 -
20c [Zn]:
Nakamura E. In Organometallic in Synthesis: A ManualSchlosser M. Wiley; Chichester: 2002. p.353 -
20d [Cu]:
Lipshutz BH. In Organometallic in Synthesis: A ManualSchlosser M. Wiley; Chichester: 2002. p.665 - 21
Yamamoto Y.Takahashi M.Miyaura N. Synlett 2002, 128 - 22
Fürstner A.Shi N. J. Am. Chem. Soc. 1996, 118: 12349 ; and references therein. - 23
Bandini M.Cozzi PG.Umani-Ronchi A. Angew. Chem. Int. Ed. 2000, 39: 2327 - 24
Bandini M.Cozzi PG.Melchiorre P.Morganti S.Umani-Ronchi A. Org. Lett. 2001, 3: 1153 - 25 Very recently, a highly stereoselective addition of 3-chloropropenyl pivaloate to aldehydes in the presence of [Cr(Salen)]-TMSCl-Mn catalytic system was reported:
Lombardo M.Licciulli S.Morganti S.Trombini C. Chem. Commun. 2003, 1762 - Recently, Grela and Blechert have reported new tailored highly active catalysts for the CM reactions, see:
-
26a
Grela K.Harutyunyan S.Michrowska A. Angew. Chem. Int. Ed. 2002, 41: 4038 -
26b
Connon SJ.Dunne AM.Blechert S. Angew. Chem. Int. Ed. 2002, 41: 3835