RSS-Feed abonnieren
DOI: 10.1055/s-2005-921899
Desymmetrization and Diastereotopic Group Selection in 1,4-Cyclohexadienes
Publikationsverlauf
Publikationsdatum:
28. November 2005 (online)
![](https://www.thieme-connect.de/media/synlett/200520/lookinside/thumbnails/10.1055-s-2005-921899-1.jpg)
Abstract
Diastereotopic group selection in 1,4-cyclohexadienes is a useful approach to synthesize rather complex compounds in a single operation. The stereoinduction occurs via a covalently bound stereogenic center. Cycloadditions, Michael additions, and radical reactions have been conducted as group-selective processes. Even more elegant is the desymmetrization of an achiral 1,4-cyclohexadiene. Various chiral reagents have been used successfully to desymmetrize 1,4-cyclohexadienes. In one step, at least two new stereogenic centers are formed. Chiral quaternary carbon centers can be obtained with high selectivity. This Account will provide an overview on diastereotopic group selection and desymmetrization in various 1,4-cyclohexadiene derivatives.
-
1 Introduction
-
2 Diastereotopic Group-Selective Processes
-
2.1 Cycloaddition
-
2.2 Michael Additions
-
2.3 Radical Processes
-
3 Desymmetrizations
-
3.1 Oxidations
-
3.2 Transition-Metal-Mediated Processes
-
3.3 Metalated Cyclohexadienes
-
4 Conclusions
Key words
asymmetric synthesis - catalysis - allylations - radical reactions - γ-butyrolactones
-
1a
Rahman Abd N.Landais Y. Curr. Org. Chem. 2002, 6: 1369 -
1b
Hoffmann RW. Synthesis 2004, 2075 - 2
Grainger RS.Tisselli P.Steed JW. Org. Biomol. Chem. 2004, 2: 151 -
3a
Wipf P.Kim Y. Tetrahedron Lett. 1992, 33: 5477 -
3b
Wipf P.Kim Y.Goldstein DM. J. Am. Chem. Soc. 1995, 117: 11106 - 4
Wipf P.Rector SR.Takahashi H. J. Am. Chem. Soc. 2002, 124: 14848 ; and references cited therein - 5
Martin SF.Campbell CL. J. Org. Chem. 1988, 53: 3184 -
6a
Bland D.Hart DJ.Lacoutiere S. Tetrahedron 1997, 53: 8871 -
6b
Bland D.Chambournier G.Dragan V.Hart DJ. Tetrahedron 1999, 55: 8953 - 7
Fujioka H.Kitagaki S.Ohno N.Kitagawa H.Kita Y.Matsumoto K. Tetrahedron: Asymmetry 1994, 5: 333 - 8
Kodama S.Hamashima Y.Nishide K.Node M. Angew. Chem. Int. Ed. 2004, 43: 2659 -
9a
Curran DP.Geib SJ.Lin C.-H. Tetrahedron: Asymmetry 1994, 5: 199 -
9b See also:
Beckwith ALJ.Roberts DH. J. Am. Chem. Soc. 1986, 108: 5893 -
10a
Curran DP.Qi H.DeMello NC.Lin C.-H. J. Am. Chem. Soc. 1994, 116: 8430 -
10b See also:
Curran DP.Lin C.-H.DeMello N.Junggebauer J. J. Am. Chem. Soc. 1998, 120: 342 - 11
Elliott MC.El Sayed NNE. Tetrahedron Lett. 2005, 46: 2957 - 12
Villar F.Kolly-Kovac T.Equey O.Renaud P. Chem.-Eur. J. 2003, 9: 1566 - 13
Nguyen TM.Seifert RJ.Mowrey DR.Lee D. Org. Lett. 2002, 4: 3959 -
14a
Angelaud R.Landais Y. J. Org. Chem. 1996, 61: 5202 -
14b
Landais Y. Chimia 1998, 52: 104 -
14c
Angelaud R.Babot O.Charvat T.Landais Y. J. Org. Chem. 1999, 64: 9613 - 15
Kolb HC.vanNieuwenhze MS.Sharpless KB. Chem. Rev. 1994, 94: 2483 - 16
Angelaud R.Landais Y.Schenk K. Tetrahedron Lett. 1997, 38: 1407 - 17
Lorenz JC.Frohn M.Zhou X.Zhang J.-R.Tang Y.Burke C.Shi Y. J. Org. Chem. 2005, 70: 2904 - 18
Sato Y.Sodeoka M.Shibasaki M. J. Org. Chem. 1989, 54: 4738 - 19
Ohrai K.Kondo K.Sodeoka M.Shibasaki M. J. Am. Chem. Soc. 1994, 116: 11737 - 20
Mori M.Takaki T.Makabe M.Sato Y. Tetrahedron Lett. 2003, 44: 3797 - 21
Honma M.Nakada M. Tetrahedron Lett. 2003, 44: 9007 -
22a
Studer A.Amrein S. Angew. Chem. Int. Ed. 2000, 39: 3080 -
22b
Studer A.Amrein S.Schleth F.Schulte T.Walton JC. J. Am. Chem. Soc. 2003, 125: 5726 - 23 For a review on the use of functionalized cyclohexadienes as radical precursors, see:
Walton JC.Studer A. Acc. Chem. Res. 2005, 38: 794 - 24
Schleth F.Vogler T.Harms K.Studer A. Chem.-Eur. J. 2004, 10: 4171 - 25
Schleth F.Studer A. Angew. Chem. Int. Ed. 2004, 43: 313 - 26
Hafner A.Duthaler RO.Marti R.Rihs G.Rothe-Streit P.Schwarzenbach F. J. Am. Chem. Soc. 1992, 114: 2321 - 27 For an excellent review on the use of TADDOLs in asymmetric synthesis, see:
Seebach D.Beck AK.Heckel A. Angew. Chem. Int. Ed. 2001, 40: 92 - 28
Noyori R.Kitamura M. Angew. Chem., Int. Ed. Engl. 1991, 30: 49 -
29a
Schleth, F., Studer, A. unpublished results
-
29b
Nagaoka H.Rutsch W.Schmid G.Iio H.Johnson MR.Kishi Y. J. Am. Chem. Soc. 1980, 102: 7965 -
29c
Fronza G.Fuganti C.Grasselli P.Pedrocchi-Fantoni G.Zirotti C. Tetrahedron Lett. 1982, 23: 4143 -
29d
Williams DR.Kingler FD. Tetrahedron Lett. 1987, 28: 869 - 30
Knoop CA.Studer A. Adv. Synth. Catal. 2005, 374: 1542 -
31a
Brieger G.Bennett JN. Chem. Rev. 1980, 80: 63 -
31b
Nicolaou KC.Snyder SA.Montagnon T.Vassilikogiannakis G. Angew. Chem. Int. Ed. 2002, 41: 1668 -
31c
Corey EJ. Angew. Chem. Int. Ed. 2002, 41: 1650 - Some examples:
-
32a
Drutu I.Njardarson JT.Wood JL. Org. Lett. 2002, 4: 493 -
32b
Miyaoka H.Yamada Y. Bull. Chem. Soc. Jpn. 2002, 75: 203 -
32c
Ng SM.Beaudry CM.Trauner D. Org. Lett. 2003, 5: 1701 - 33
Takacs JM.Helle MA.Seely FL. Tetrahedron Lett. 1986, 27: 1257 - Reviews:
-
36a
Fürstner A. Angew. Chem. Int. Ed. 2000, 39: 3012 -
36b
Trnka TM.Grubbs RH. Acc. Chem. Res. 2001, 34: 18 -
36c
Connon SJ.Blechert S. Top. Organomet. Chem. 2004, 11: 93 -
36d
Grubbs RH. Tetrahedron 2004, 60: 7117 -
36e
Nicolaou KC.Bulger PG.Sarlah D. Angew. Chem. Int. Ed. 2005, 44: 4490 -
37a
Dewi P.Randl S.Blechert S. Tetrahedron Lett. 2005, 46: 577 - See also:
-
37b
Funk TW.Efskind J.Grubbs RH. Org. Lett. 2005, 7: 187 -
37c
Paquette LA.Basu K.Eppich JC.Hofferberth JE. Helv. Chim. Acta 2002, 85: 3033
References
The enantiomeric excess was determined by chiral HPLC.
35Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as private communication no. CCDC-280946 [Klaus Harms, Private Communication(1078), 2005]. Copies of the data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road Cambridge CB2 1EZ, UK).