RSS-Feed abonnieren
DOI: 10.1055/s-2006-948180
Transposition of Allylic Alcohols into Carbonyl Compounds Catalyzed by Rhodium-Phosphinine Complexes
Publikationsverlauf
Publikationsdatum:
09. August 2006 (online)
Abstract
The isomerization of a variety of allylic alcohols with formation of the corresponding saturated carbonyl compounds is readily accomplished by a new catalyst system comprising rhodium and a trisubstituted phosphinine (phosphabenzene derivative), especially when the Rh complex is activated by hydrogen prior to the transposition reaction.
Key words
green chemistry - homogeneous catalysis - isomerization - phosphorus - rhodium
- 1
Reetz MT.Guo H. Beilstein J. Org. Chem. 2005, 1:3 - Reviews:
-
2a
Uma R.Crévisy C.Grée R. Chem. Rev. 2003, 103: 27 -
2b
van der Drift RC.Bouwman E.Drent E. J. Organomet. Chem. 2002, 650: 1 - Leading studies regarding Rh- and Ru-catalyzed isomerization of allylic alcohols:
-
3a
Trost BM.Kulawiec RJ. J. Am. Chem. Soc. 1993, 115: 2027 -
3b
McGrath DV.Grubbs RH. Organometallics 1994, 13: 224 -
3c
Markó IE.Gautier A.Tsukazaki M.Llobet A.Plantalech-Mir E.Urch CJ.Brown SM. Angew. Chem. Int. Ed. 1999, 38: 1960 ; Angew. Chem. 1999, 111, 2126 -
3d
Slugovc C.Rüba E.Schmid RD.Kirchner K. Organometallics 1999, 18: 4230 -
3e
de Bellefon C.Caravieilhes S.Kuntz G. C. R. Acad. Sci., Ser. IIc: Chim. 2000, 3: 607 -
3f
Tanaka K.Fu GC. J. Org. Chem. 2001, 66: 8177 -
3g
Uma R.Davies MK.Crévisy C.Grée R. Eur. J. Org. Chem. 2001, 3141 -
3h
Cadierno V.García-Garrido SE.Gimeno J. Chem. Commun. 2004, 232 -
3i
Martín-Matute B.Bogár K.Edin M.Kaynak FB.Bäckvall J.-E. Chem. Eur. J. 2005, 11: 5832 -
3j
Crochet P.Díez J.Fernández-Zúmel MA.Gimeno J. Adv. Synth. Catal. 2006, 348: 93 -
3k
Ito M.Kitahara S.Ikariya T. J. Am. Chem. Soc. 2005, 127: 6172 -
3l
Takai Y.Kitaura R.Nakatani E.Onishi T.Kurosawa H. Organometallics 2005, 24: 4729 -
3m
Cadierno V.García-Garrido SE.Gimeno J.Varela-Álvarez A.Sordo JA. J. Am. Chem. Soc. 2006, 128: 1360 - 4
Reetz MT.Li X. Angew. Chem. Int. Ed. 2005, 44: 2962 ; Angew. Chem. 2005, 117, 3022 -
5a
Breit B. Chem. Commun. 1996, 2071 -
5b
Breit B.Winde R.Mackewitz T.Paciello R.Harms K. Chem. Eur. J. 2001, 7: 3106 - 6
Knoch F.Kremer F.Schmidt U.Zenneck U.LeFloch P.Mathey F. Organometallics 1996, 15: 2713
References and Notes
General Procedure for the Isomerization of Allylic Alcohol.
A dry 5-mL Schlenk flask under an atmosphere of argon was charged with a 5.4 mM solution of P-ligand (0.5 mL) in dry CH2Cl2 and a 5.4 mM solution of [Rh(NBD)2]BF4 (0.25 mL) in CH2Cl2. The mixture was stirred for 30 min at r.t., then stirred for an additional 30 min under 1.3 bar H2. The CH2Cl2 and H2 were removed by Ar displacement under reduced pressure, then 0.5 mL of CH2Cl2 and a 67.5 mM solution of an allylic alcohol in CH2Cl2 (1 mL) were added. The isomerization was carried out for the periods given. The reaction solution was passed through a small amount of silica gel and selectivity and conversion were determined by gas chromatography (GC and GC-MS).