RSS-Feed abonnieren
DOI: 10.1055/s-2001-16095
A One-Pot Conversion of Carboxylic Acids into Homoallylic Alcohols
Publikationsverlauf
Publikationsdatum:
23. September 2004 (online)
![](https://www.thieme-connect.de/media/synthesis/200110/lookinside/thumbnails/10.1055-s-2001-16095-1.jpg)
Abstract
A one-pot procedure for the conversion of carboxylic acids into homoallylic alcohols under remarkably mild and selective conditions is described. The triethylammonium salts of alkanoic acids are treated with Bu3P/PhSeCl to afford the corresponding acyl selenides that are reduced to aldehydes by tributyltin hydride under radical conditions. Direct in situ trapping of the aldehydes by allylboronates affords the desired homoallylic alcohols. Preparation of optically active alcohols by use of a tartrate-modified allylboronate is possible and the enantioselectivities are similar to the ones obtained when isolated aldehydes are employed.
Key words
radicals - allylboronates - acyl selenides - allylation - carboxylic acid - reduction
- 2
Yamamoto Y.Asao N. Chem. Rev. 1993, 93: 2207 - 3
Roush WR. In Comprehensive Organic Chemistry Vol. 2:Trost BM.Fleming I.Heatcook CH. Pergamon Press; Oxford: 1991. p.1 -
4a
Roush WR. In Houben-Weyl, Stereoselective Synthesis Vol E21:Helmchen G.Hoffman WR.Mulzer J.Schaumann E. Thieme; Stuttgart: 1995. p.1410 -
4b
Matteson DS. Stereodirected Synthesis with Organoboranes Springer-Verlag; Berlin: 1995. - Via Weinreb amides:
-
5a
Nahm S.Weinreb SM. Tetrahedron Lett. 1981, 22: 3815 -
5b
Fehrentz J.-A.Castro B. Synthesis 1983, 676 -
5c
Goel OP.Krolls U.Stier M.Kesten S. Org. Synth. 1988, 67: 69 -
5d Via thioesters:
Fukuyama T.Lin S.-C.Li L. J. Am. Chem. Soc. 1990, 112: 7050 -
5e Via TMS esters:
Chandrasekhar S.Kumar MS.Muralidkar B. Tetrahedron Lett. 1998, 39: 909 -
5f Via reduction/oxidation:
Brown HC.Rao CG.Kulkarni SU. Synthesis 1979, 704 - 6
Batty D.Crich D. Synthesis 1990, 273 -
7a The reduction of acyl selenides to aldehydes is well established:
Pfenninger J.Heuberger C.Graf W. Helv. Chim. Acta 1980, 63: 2328 ; however, this reaction is not commonly used for preparative purposes -
7b For a comprehensive review on acyl radical chemistry, see:
Chatgilialoglu C.Crich D.Komatsu M.Ryu I. Chem. Rev. 1999, 1991 -
8a
Hoffmann RW.Endesfelder A.Zeiss H.-J. Carbohydr. Res. 1983, 123: 320 -
8b
Hoffmann RW.Weidmann U. Chem. Ber. 1985, 118: 3966 -
8c
Roush WR.Adam MA.Walts AE.Haris DJ. J. Am. Chem. Soc. 1986, 108: 3422 -
8d
Hoffmann WR.Metternich R.Lanz JW. Liebigs Ann. Chem. 1987, 881 -
8e
Hoffmann RW.Wolff JJ. Chem. Ber. 1991, 124: 563 -
8f
Jego JM.Carboni B.Vaultier M. Bull. Soc. Chim. Fr. 1992, 554 -
8g
Hoffmann RW.Stiasny H.-C.Krueger J. Tetrahedron 1996, 52: 7421 -
8h
Cavallaro CL.Herpin T.McGuinness BF.Shimshock YC.Dolle RE. Tetrahedron Lett. 1999, 40: 2411 -
9a
Roush WR.Walts AE.Hoong LK. J. Am. Chem. Soc. 1985, 107: 8186 -
9b
Roush WR.Kageyama MA. Tetrahedron Lett. 1985, 26: 4327 -
9c
Roush WR.Straub JA. Tetrahedron Lett. 1986, 27: 3349 -
9d
Roush WR.Palkowitz AD. J. Am. Chem. Soc. 1987, 109: 953 -
9e
Roush WR.Park JC. J. Org. Chem. 1990, 55: 1143 -
9f
Roush WR.Hoong LK.Palmer MAJ.Park JC. J. Org. Chem. 1990, 55: 4109 -
9g
Roush WR.Hoong LK.Palmer MAJ.Straub JA.Palkowitz AD. J. Org. Chem. 1990, 55: 4117 -
9h
Roush WR.Ando K.Powers DB.Palkowitz AD.Halterman RL. J. Am. Chem. Soc. 1990, 112: 6339 -
9i
Roush WR.Palkowitz AD.Ando K. J. Am. Chem. Soc. 1990, 112: 6348 -
9j
Roush WR.Straub JA.VanNieuwenhze MS. J. Org. Chem. 1991, 56: 1636 -
9k
Roush WR.Lin X.Straub JA. J. Org. Chem. 1991, 56: 1649 -
9l
Roush WR.Park JC. Tetrahedron Lett. 1991, 32: 6285 -
9m
Roush WR.Hunt JA. J. Org. Chem. 1995, 60: 798 - Kinetic studies:
-
10a
Fischer H.Henning P. Acc. Chem. Res. 1987, 20: 200 -
10b
Tsentalovich YP.Fisher H. J. Chem. Soc., Perkin Trans. 2 1994, 729 -
10c
Chatgilialoglu C.Ferreri C.Lucarini M.Pedrielli P.Pedulli GF. Organometallics 1995, 14: 2672 - Synthetic applications:
-
11a
Pfenninger J.Graf W. Helv. Chim. Acta 1980, 63: 2328 -
11b
Quinrante J.Escolano C.Bonjoch J. Synlett 1997, 179 -
11c
Stojanovic A.Renaud P. Synlett 1997, 181 - 13
Wuts PGM.Jung Y.-W. J. Org. Chem. 1991, 56: 365 - 14
Renaud P.Lacôte E.Quaranta L. Tetrahedron Lett. 1998, 39: 2123 - 15
Jones P.Knochel P. J. Org. Chem. 1999, 64: 186 - 16
Reindel F.Niederlander K. Chem. Ber. 1935, 68: 1243 - 17
Bartlett PA.Johnson WS.Elliott JD. J. Am. Chem. Soc. 1983, 105: 2088
References
New address: Department für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3000 Bern 9, Switzerland. E-mail: philippe.renaud@ioc.unibe.ch.
12Roush (ref. [9f] ) has reported that allylation reactions are usually higher yielding in toluene than in THF.