Subscribe to RSS
Download PDF
DOI: 10.1055/s-2003-38760
(-)-Sparteine in Asymmetric Synthesis
Publication History
Publication Date:
17 April 2003 (online)
Introduction
Asymmetric synthesis represents a challenging topic in modern organic chemistry. The asymmetric deprotonation of a prochiral carbon by a chiral base offers attractive access to a chiral carbanion, which may react to give enantioenriched products. (-)-Sparteine is a chiral bidentate ligand with broad applicability. Hoppe was the first to use a mixture of alkyllithium and (-)-sparteine (Figure 1) for very effective asymmetric deprotonations. [1] Beak examined enantioselective deprotonations of N-Boc-pyrrolidines and N-Boc-allylamines. [2] Furthermore, it was used for dynamic resolutions [3] and deprotonations [4] of phosphine-boranes, for asymmetric additions of alkyllithiums to imines, [5] for asymmetric carbometallations of cinnamyl derivatives, [6] for palladium-catalyzed oxidative kinetic resolutions of secondary alcohols, [7] and for enantioselective syntheses of ferrocenes with planar chirality. [8]
The title compound is an alkaloid, which can be isolated from certain papilionaceous plants such as Scotch broom. [9] Its antipode is also naturally occurring but can be obtained far less easily. An 18 steps asymmetric total synthesis of (+)-sparteine starting from norbornadiene has been reported. [10] A (+)-sparteine surrogate is readily available from (-)-cytisine. [11]
(-)-Sparteine is commercially available as a free base or as the sulfate-pentahydrate. The chiral ligand can usually be recovered from the reaction mixtures by alkaline extraction.
Figure 1
- 1a
Hoppe D.Zschage O. Angew.Chem. Int. Ed. 1989, 28: 69 - 1b
Hoppe D.Hintze F.Tebben P. Angew. Chem. Int. Ed. 1990, 29: 1422 - 1c
Hoppe D. In Encyclopedia of Reagents for Organic Synthesis Vol. 7:Paquette LA. Wiley; Chichester: 1995. p.4662 - 1d
Hoppe D.Hense T. Angew. Chem. Int. Ed. 1997, 36: 2282 - 1e
Özlügedik M.Kristensen J.Wibbeling B.Fröhlich R.Hoppe D. Eur. J. Org. Chem. 2002, 414 - 1f
Hoppe D. In Topics in Organometallic ChemistryHodgson DM. Springer; Heidelberg: 2003. Vol. 5. p.61 - 2a
Kerrick ST.Beak P. J. Am. Chem. Soc. 1991, 113: 9708 - 2b
Weisenburger GA.Beak P. J. Am. Chem. Soc. 1996, 118: 12218 - 2c
Beak P.Basu A.Gallagher DJ.Park YS.Thayumanavan S. Acc. Chem. Res. 1996, 29: 552 - 2d
Basu A.Thayumanavan S. Angew. Chem. Int. Ed. 2002, 41: 717 - 3
Wolfe B.Livinghouse T. J. Am. Chem. Soc. 1998, 120: 5116 - 4a
Nagata K.Matsukawa S.Imamoto T. J. Org. Chem. 2000, 65: 4185 - 4b
Wolfe B.Livinghouse T. J. Org. Chem. 2001, 66: 1514 - 5
Denmark SE.Nakajima N.Nicaise OJ.-C. J. Am. Chem. Soc. 1994, 116: 8797 - 6a
Klein S.Marek I.Poisson JF.Normant JF. J. Am. Chem. Soc. 1995, 117: 8853 - 6b
Norsikian S.Marek I.Klein S.Poisson JF.Normant JF. Chem.-Eur. J. 1999, 5: 2055 - 7a
Jensen DR.Pugsley JS.Sigman MS. J. Am. Chem. Soc. 2001, 123: 7475 - 7b
Ferreira EM.Stoltz BM. J. Am. Chem. Soc. 2001, 123: 7725 - 8a
Tsukazaki M.Tinkl M.Roglans A.Chapell BJ.Taylor NJ.Snieckus V. J. Am. Chem. Soc. 1996, 118: 685 - 8b
Metallinos C.Snieckus V. Org. Lett. 2002, 4: 1935 - 9a
Stenhouse J. Ann. Chem. Pharm. 1851, 78: 1 - 9b
Mills EJ. Ann. Chem. Pharm. 1863, 125: 71 - 9c
Boczo W. Heterocycles 1992, 33: 1101 - 10
Smith BT.Wendt JA.Aubé J. Org. Lett. 2002, 4: 2577 - 11
Dearden MJ.Firkin CR.Hermet J.-PR.O’Brien PJ. J. Am. Chem. Soc. 2002, 124: 11870 - 12
Kise N.Urai T.Yoshida J. Tetrahedron: Asymmetry 1998, 9: 3125 - 13a
Bailey WF.Mealy MJ. J. Am. Chem. Soc. 2000, 122: 6787 - 13b
Sanz Gil G.Groth U. J. Am. Chem. Soc. 2000, 122: 6789 - 14
Barluenga J.Fañanás FJ.Sanz R.Marcos C. Org. Lett. 2002, 4: 2225 - 15
MacMillan JB.Molinski TF. Org. Lett. 2002, 4: 1883 - 16
Shintani R.Fu GC. Angew. Chem. Int. Ed. 2002, 41: 1057 - 17a
Hodgson DM.Lee GP.Marriott RE.Thompson AJ.Wisedale R.Witherington J. J. Chem. Soc., Perkin Trans. 1 1998, 2151 - 17b
Hodgson DM.Maxwell CR.Miles TJ.Paruch E.Stent MAH.Matthews IR.Wilson FX.Witherington J. Angew. Chem. Int. Ed. 2002, 41: 4313