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Synthesis 2006(13): 2233-2241
DOI: 10.1055/s-2006-942417
DOI: 10.1055/s-2006-942417
PAPER
© Georg Thieme Verlag Stuttgart · New York
Development of a Catalytic Asymmetric Variant of Hoppe’s O-Alkyl Carbamate Deprotonation Methodology
Weitere Informationen
Received
24 March 2006
Publikationsdatum:
12. Juni 2006 (online)
Publikationsverlauf
Publikationsdatum:
12. Juni 2006 (online)
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Abstract
The optimisation of a ligand-exchange approach to catalytic asymmetric deprotonation of O-alkyl carbamates and subsequent electrophilic trapping (the ‘Hoppe reaction’) is presented. The method uses s-BuLi and sub-stoichiometric amounts of a chiral diamine [(-)-sparteine or the (+)-sparteine surrogate] in conjunction with an achiral ‘regenerating’ diamine (bisisopropyl bispidine) for the deprotonation and proceeds with good yields (up to 84%) and high enantioselectivity (up to 94:6 er). The first applications of this catalytic asymmetric deprotonation methodology in natural product synthesis are also described.
Key words
asymmetric catalysis - synthesis - organometallic reagents - chiral bases - diamines
- 1
Hoppe D.Hintze F.Tebben P. Angew. Chem., Int. Ed. Engl. 1990, 29: 1422 - For reviews, see:
-
2a
Hoppe D.Hense T. Angew. Chem., Int. Ed. Engl. 1997, 36: 2282 -
2b
Hoppe D.Christoph G. The Chemistry of Organolithium Compounds In The Chemistry of Functional GroupsRappoport Z.Marek I. Wiley; Chichester: 2004. p.1077 - For selected representative examples, see:
-
3a
Sommerfeld P.Hoppe D. Synlett 1992, 764 -
3b
Guarnieri W.Grehl M.Hoppe D. Angew. Chem., Int. Ed. Engl. 1994, 33: 1734 -
3c
Paetow M.Kotthaus M.Grehl M.Fröhlich R.Hoppe D. Synlett 1994, 1034 -
3d
Haller J.Hense T.Hoppe D. Liebigs Ann. 1996, 489 -
3e
Woltering MJ.Fröhlich R.Hoppe D. Angew. Chem., Int. Ed. Engl. 1997, 36: 1764 -
3f
Guarnieri W.Sendzik M.Fröhlich R.Hoppe D. Synthesis 1998, 1274 -
3g
Sendzik M.Guarnieri W.Hoppe D. Synthesis 1998, 1287 -
3h
Woltering MJ.Fröhlich R.Wibbeling B.Hoppe D. Synlett 1998, 797 -
3i
Oestreich M.Fröhlich R.Hoppe D. Tetrahedron Lett. 1998, 39: 1745 -
3j
Weber B.Schwerdtfeger J.Fröhlich R.Göhrt R.Hoppe D. Synthesis 1999, 1915 -
3k
Christoph G.Hoppe D. Org. Lett. 2002, 4: 2189 -
3l
Gralla G.Wibbeling B.Hoppe D. Org. Lett. 2002, 4: 2193 -
3m
Gralla G.Wibbeling B.Hoppe D. Tetrahedron Lett. 2003, 44: 8979 - 4
Hintze F.Hoppe D. Synthesis 1992, 1216 - 5
Paetow M.Ahrens H.Hoppe D. Tetrahedron Lett. 1992, 33: 5323 - 6
Menges M.Brückner R. Eur. J. Org. Chem. 1998, 1023 - 7
Papillon JPN.Taylor RJK. Org. Lett. 2002, 4: 119 - 8
Genet C.McGrath MJ.O’Brien P. Org. Biomol. Chem. 2006, 4: 1376 - 9
Würthwein E.-U.Hoppe D. J. Org. Chem. 2005, 70: 4443 - 10
Dearden MJ.Firkin CR.Hermet J.-PR.O’Brien P. J. Am. Chem. Soc. 2002, 124: 11870 - 11
Beak P.Kerrick ST.Wu S.Chu J. J. Am. Chem. Soc. 1994, 116: 3231 - 12
McGrath MJ.O’Brien P. J. Am. Chem. Soc. 2005, 127: 16378 - For examples of ligand exchange with (-)-sparteine, see:
-
13a
Wilhelm R.Widdowson DA. Org. Lett. 2001, 3: 3079 -
13b
Rutherford JL.Hoffmann D.Collum DB. J. Am. Chem. Soc. 2002, 124: 264 - 14
Basu A.Thayumanavan S. Angew. Chem. Int. Ed. 2002, 41: 716 -
15a
Hermet J.-PR.Porter DW.Dearden MJ.Harrison JR.Koplin T.O’Brien P.Parmene J.Tyurin V.Whitwood AC.Gilday J.Smith NM. Org. Biomol. Chem. 2003, 1: 3977 -
15b
Dixon AJ.McGrath MJ.O’Brien P. Org. Synth. 2006, 83: 141 -
16a
Larrow JF.Jacobsen EN. Org. Synth. 1998, 75: 1 -
16b
Benson SC.Cai P.Colon M.Haiza MA.Tokles M.Snyder JK. J. Org. Chem. 1988, 53: 5335 - 17
O’Brien P.Wiberg KB.Bailey WF.Hermet J.-PR.McGrath MJ. J. Am. Chem. Soc. 2004, 126: 15480 - 18
Dearden MJ.McGrath MJ.O’Brien P. J. Org. Chem. 2004, 69: 5789 - 19
Huttenloch O.Laxman E.Waldmann H. Chem. Eur. J. 2002, 8: 4767 - 20
Lesma G.Danieli B.Passarella D.Sacchetti A.Silvani A. Tetrahedron: Asymmetry 2003, 14: 2453 - 21
Garrison GL.Berlin KD.Scherlag BJ.Lazzara R.Patterson E.Fazekas T.Sangiah S.Chen C.-L.Schubot FD.van der Helm D. J. Med. Chem. 1996, 39: 2559 - 22
McGrath MJ.Bilke J.O’Brian P. Chem. Commun. 2006, 2607 - 23
Trost BM.Kulawiec RJ. J. Am. Chem. Soc. 1993, 115: 2027 - 24
Hoppe D.Paetow M.Hintze F. Angew. Chem., Int. Ed. Engl. 1993, 32: 394 - 25
Wang FD.Yue J.-M. Eur. J. Org. Chem. 2005, 2575 - 26
Hambley TW.Rideout J.Taylor WC. Aust. J. Chem. 1990, 43: 1327 - 27
Beckmann E.Desai V.Hoppe D. Synlett 2004, 2275 - 28
Huang J.O’Brien P. Synthesis 2006, 425 - 29
Nikolic A.Beak P. Org. Synth. 1996, 73: 23 - 30
Behrens K.Fröhlich R.Meyer O.Hoppe D. Eur. J. Org. Chem. 1998, 2397 - 31
Tomooka K.Shimizu H.Inoue T.Shibata H.Nakai T. Chem. Lett. 1999, 759