Subscribe to RSS
DOI: 10.1055/s-2004-817779
Development of the First Practical Catalyst for the Asymmetric Addition of Alkyl- and Arylzinc Reagents to Ketones
Publication History
Publication Date:
17 February 2004 (online)
Abstract
A long-standing problem in organic synthesis is the catalytic asymmetric addition of alkyl groups to ketones to establish chiral quaternary centers. Such compounds are valuable chiral building blocks that can be further elaborated. In this account, we describe the previously unreported story of the development of the first effective catalyst for the enantioselective addition of dialkyl- and diphenylzinc reagents to ketones. The scope of this reaction is outlined, including a tandem enantioselective addition to cyclic enones/diastereoselective epoxidation protocol that establishes three contiguous stereocenters in a one-pot procedure.
-
1 Introduction
-
1.1 Asymmetric Catalysis with Ketones
-
1.2 Prior Art
-
2 Our Approach to Catalyst Development
-
2.1 Asymmetric Alkylation of Ketones
-
2.2 Generation I Catalysts
-
2.3 Generation II Catalysts
-
2.4 Generation III Catalysts - Third Time’s a Charm!
-
3 Asymmetric Additions to Cyclic Conjugated Enones-Tandem Asymmetric Alkylation/Epoxidation Reactions
-
4 Asymmetric Phenylation of Ketones
-
5 Summary
Key words
alcohols - alkylations - asymmetric catalysis - ketones - quaternary centers
- 1
Oguni N.Omi T. Tetrahedron Lett. 1984, 25: 2823 - 2
Oguni N.Matsuda Y.Kaneko T. J. Am. Chem. Soc. 1988, 110: 7877 - 3
Kitamura M.Okada S.Suga S.Noyori R. J. Am. Chem. Soc. 1989, 11: 4028 - 4
Kitamura M.Suga S.Oka H.Noyori R. J. Am. Chem. Soc. 1998, 120: 9800 - 5
Noyori R.Kitamura M. Angew. Chem. Int. Ed. 1991, 30: 49 - 6
Pu L.Yu H.-B. Chem. Rev. 2001, 101: 757 - 7
Oppolzer W.Radinov RN. Helv. Chim. Acta 1992, 75: 170 - 8
Oppolzer W.Radinov RN. J. Am. Chem. Soc. 1993, 115: 1593 - 9
Oppolzer W.Radinov RN.Brabander JD. Tetrahedron Lett. 1995, 36: 2607 - 10
Oppolzer W.Radinov RN.El-Sayed E. J. Org. Chem. 2001, 66: 4766 - 11
Wipf P.Ribe S. J. Org. Chem. 1998, 63: 6454 - 12
Wipf P.Kendall C. Chem.-Eur. J. 2002, 8: 1778 - 13
Dahmen SD.Bräse S. Org. Lett. 2001, 3: 4119 - 14
Chen YK.Lurain AE.Walsh PJ. J. Am. Chem. Soc. 2002, 124: 12225 - 15
Boyall D.Frantz DE.Carreira EM. Org. Lett. 2000, 4: 2605 - 16
Boyall D.López F.Sasaki H.Frantz D.Carreira EM. Org. Lett. 2000, 2: 4233 - 17
Anand NK.Carreira EM. J. Am. Chem. Soc. 2001, 123: 9687 - 18
Dosa PI.Fu GC. J. Am. Chem. Soc. 1998, 120: 445 - 19
Ramón DJ.Yus M. Tetrahedron Lett. 1998, 39: 1239 - 20
Ramón DJ.Yus M. Tetrahedron 1998, 54: 5651 - 21
Kitamura M.Suga S.Kawai K.Noyori R. J. Am. Chem. Soc. 1986, 108: 6071 - 22
Noyori R.Suga S.Kawai K.Okada S.Kitamura M. Pure Appl. Chem. 1988, 60: 1597 - 23
Noyori R. Asymmetric Catalysis in Organic Synthesis Wiley; New York: 1994. - 24
Dosa PI.Ruble JC.Fu GC. J. Org. Chem. 1997, 62: 444 - 25
Bolm C.Muñiz K. J. Chem. Soc., Chem. Commun. 1999, 1295 - 26
Bolm C.Hermanns N.Hildebrand JP.Muñiz K. Angew. Chem. Int. Ed. 2000, 39: 3465 - 27
Bolm C.Hildebrand JP.Muñiz K.Hermanns N. Angew. Chem. Int. Ed. 2001, 40: 3284 - 28
Bolm C.Rudolph J. J. Am. Chem. Soc. 2002, 124 - 29
Huang W.-S.Pu L. J. Org. Chem. 1999, 64: 4222 - 30
Huang W.-S.Pu L. Tetrahedron Lett. 2000, 41: 145 - 31
Takahashi H.Kawakita T.Ohno M.Yoshioka M.Kobayashi S. Tetrahedron 1992, 48: 5691 - 32
Takahashi H.Kawakita T.Yoshioka M.Kobayashi S.Ohno M. Tetrahedron Lett. 1989, 30: 7095 - 33
Seebach D.Beck AK.Heckel A. Angew. Chem. Int. Ed. 2001, 40: 92 - 34
Seebach D.Beck AK.Schmidt B.Wang YM. Tetrahedron 1994, 50: 4363 - 35
Weber B.Seebach D. Angew. Chem. Int. Ed. 1992, 31: 84 - 36
DiMauro EF.Kozlowski MC. Org. Lett. 2002, 4: 3781 - 37
DiMauro EF.Kozlowski MC. J. Am. Chem. Soc. 2002, 124: 12668 - 38
Coppola GM.Schuster HF. α-Hydroxy Acids in Enantioselective Synthesis VCH; Weinhein: 1997. - 39
Funabashi K.Jachmann M.Kanai M.Shibasaki M. Angew. Chem. Int. Ed. 2003, 42: 5489 - 40
Jiang B.Chen Z.Tang X. Org. Lett. 2002, 4: 3451 - 41
Cozzi PG. Angew. Chem. Int. Ed. 2003, 42: 2895 - 42
Balsells J.Costa AM.Walsh PJ. Isr. J. Chem. 2001, 41: 251 - 43
Balsells J.Betancort JM.Walsh PJ. Angew. Chem. Int. Ed. 2000, 39: 3428 - 44
Pritchett S.Gantzel P.Walsh PJ. Organometallics 1997, 16: 5130 - 45
Pritchett S.Woodmansee DH.Davis TJ.Walsh PJ. Tetrahedron Lett. 1998, 39: 5941 - 46
Walsh PJ. Acc. Chem. Res. 2003, 36: 739 - 47
Ostwald R.Chavant P.-Y.Stadtmuller H.Knochel P. J. Org. Chem. 1994, 59: 4143 - 48
Pritchett S.Woodmansee DH.Gantzel P.Walsh PJ. J. Am. Chem. Soc. 1998, 120: 6423 - 49
Ho DE.Betancort JM.Woodmansee DH.Larter ML.Walsh PJ. Tetrahedron Lett. 1997, 38: 3867 - 50
Balsells J.Walsh PJ. J. Am. Chem. Soc. 2000, 122: 3250 - 51
Balsells J.Davis TJ.Carroll PJ.Walsh PJ. J. Am. Chem. Soc. 2002, 124: 10336 - 52
García C.LaRochelle LK.Walsh PJ. J. Am. Chem. Soc. 2002, 124: 10970 - 53
Yus M.Ramón DJ.Prieto O. Tetrahedron: Asymmetry 2002, 13: 2291 - 54
Jeon S.-J.Walsh PJ. J. Am. Chem. Soc. 2003, 125: 9544 - 55
Hoveyda AH.Evans DA.Fu GC. Chem. Rev. 1993, 93: 1307 - 56
Seyferth D. Organometallics 2001, 20: 2940 - 57
Lewinski J.Ochal Z.Bojarski E.Tratkiewicz E.Justyniak I.Lipkowski J. Angew. Chem. Int. Ed. 2003, 42: 4643 - 58
Lewinski J.Marciniak W.Lipkowski J.Justyniak I. J. Am. Chem. Soc. 2003, 125: 12698 - 59
Yamamoto K.Yamamoto N. Chem. Lett. 1989, 1149 - 60
Enders D.Zhu JQ.Raabe G. Angew. Chem. Int. Ed. 1996, 35: 1725 - 61
Enders D.Zhu JQ.Kramps L. Liebigs Ann. Chem. 1997, 1101 - 62
Yu H.-B.Zheng X.-F.Lin Z.-M.Hu Q.-S.Huang W.-S.Pu L. J. Org. Chem. 1999, 64: 8149 - 63
Enders D.Kramps L.Zhu J. Tetrahedron: Asymmetry 1998, 9: 3959 - 64
van der Deen H.Kellogg RM.Feringa BL. Org. Lett. 2000, 2: 1593 - 65
Yus M.Ramón DJ.Prieto O. Eur. J. Org. Chem. 2003, 2745 - 66
García C.Walsh PJ. Org. Lett. 2003, 5: 3641 - 67
Prieto O.Ramón DJ.Yus M. Tetrahedron: Asymmetry 2003, 14: 1955