Abstract
Enantioselective desymmetrisation is one of the most effective
strategies for asymmetric synthesis. Typically, a meso starting
material with an internal mirror plane is desymmetrised by reaction
with a chiral reagent; excellent yields of products as single enantiomers
may be obtained. In fact, this approach is amenable to the synthesis
of compounds with any embedded improper element of symmetry (such
as a centre of symmetry). This review concentrates on the strategies,
which are available for the synthesis of centrosymmetric (and S
4 -symmetric) molecules and
describes methods for their desymmetrisation. Examples of syntheses
of biologically active molecules and natural products are used.
Key words
asymmetric synthesis - desymmetrisation - internal mirror
plane - natural product synthesis
References
1a
Mori Y.
Yaegashi K.
Furukawa H.
J. Am. Chem. Soc.
1997,
119:
4557
1b
Rainier JD.
Allwein SP.
Cox JM.
J. Org. Chem.
2001,
66:
1380
2
Nicolaou KC.
Yang Z.
Shi G.
Gunzner JL.
Agrios KA.
Gartner P.
Nature (London)
1998,
392:
264
3a
Nicolaou KC.
Angew. Chem., Int.
Ed. Engl.
1996,
35:
589
3b
Nicolaou KC.
Rutjes FPJT.
Theodorakis EA.
Tiebes J.
Sato M.
Untersteller E.
J.
Am. Chem. Soc.
1995,
117:
10252
4a
Hirama M.
Oishi T.
Uehara H.
Inoue M.
Maruyama M.
Oguri H.
Satake M.
Science
2001,
294:
1904
4b
Inoue M.
Uehara H.
Maruyama M.
Hirama M.
Org. Lett.
2002,
4:
4551
5a
Fuwa H.
Kainuma N.
Tachibana K.
Sasaki M.
J. Am. Chem.
Soc.
2002,
124:
14983I
5b
Kadota I.
Takamura H.
Sato K.
Ohno A.
Matsuda K.
Yamamoto Y.
J. Am. Chem. Soc.
2003,
125:
46
6a
Nicolaou KC.
Reddy KR.
Skokotas G.
Sato F.
Xiao X.-Y.
J. Am. Chem.
Soc.
1992,
114:
7935
6b
Nicolaou KC.
Reddy KR.
Skokotas G.
Sato F.
Xiao X.-Y.
Hwang C.-K.
J. Am. Chem. Soc.
1993,
115:
3558
6c
Morimoto M.
Matsukura H.
Nakata T.
Tetrahedron
Lett.
1996,
37:
6365
6d
Kadota I.
Yamamoto Y.
J. Org. Chem.
1998,
63:
6597
6e
Kadota I.
Jung-Youl P.
Koumura N.
Pollaud G.
Maksukawa Y.
Yamamoto Y.
Tetrahedron Lett.
1995,
36:
5777
7a Hayward MM. inventors; WO patent 0102787.
7b Blumberg LC, Brown MF, McGlynn MA, Poss CS, and Gladue RP. inventors; WO patent 0172728.
8 Maw GN. inventors; GB
patent 2374074.
9 Iwata M, Kawano N, Kaizawa H, Takuwa T, Tsukamoto I, Seo R, Yahiro K, Kobayashi M, and Takeuchi M. inventors; WO patent 0102778.
10 Chang KJ, Pendergast W, Biciunas KP, and Wu ES.-C. inventors; US patent 20020052007.
11 Beierlein K, Bremberg U, Caldirola P, Jenmalm Jensen A, Johansson G, Mott A, Tedenborg L, and Thor M. inventors; WO patent 0100822.
12a Wang T, Wallace OB, Zhang Z, Meanwell NA, and Bender JA. inventors; WO patent 0162255.
12b Wang T, Wallace OB, Zhang Z, Meanwell NA, and Bender JA. inventors; US patent 2002119982.
13
Aitcher TD.
Anderson RC.
Gao J.
Shetty SS.
Coppola GM.
Stanton JL.
Knorr DC.
Sperbeck DM.
Brand LJ.
Vinluan CC.
Kaplan EL.
Dragland CJ.
Tomaselli HC.
Islam A.
Lozito RJ.
Liu X.
Maniara WM.
Fillers WS.
DelGrande D.
Walter RE.
Mann WR.
J.
Med. Chem.
2000,
43:
236
14a
Calderon SN.
RiceK KC.
Rothman RB.
Porreca F.
Flippen-Anderson JL.
Kayakiri H.
Xu H.
Becketts K.
Smith LE.
Bilsky EJ.
Davis P.
Horvath R.
J. Med. Chem.
1997,
40:
695
14b
Katsura Y.
Zhang X.
Homma K.
Rice KC.
Calderon SN.
Rothmann R.
Yamamura HI.
Davis P.
Flippen-Anderson JL.
Xu H.
Becketts K.
Flotz EJ.
Porreca F.
J. Med. Chem.
1997,
40:
2936
15
Willis MC.
J.
Chem Soc., Perkin Trans. 1
1999,
1765
16
Janetka JW.
Furness MS.
Zhang X.
Coop A.
Folk JE.
Mattson MV.
Jacobson AE.
Rice KC.
Becketts K.
J. Org. Chem.
2003,
68:
3976
17a
Fujiwara K.
Morishita H.
Saki K.
Murai A.
Tetrahedron
Lett.
2000,
41:
507
17b
Mori Y.
Mitsuoka S.
Furukawa H.
Tetrahedron
Lett.
2000,
41:
4161
18
Matsuo G.
Hinou H.
Koshino H.
Suenaga T.
Nakata T.
Tetrahedron
Lett.
2000,
41:
903
19a
Gerlach H.
Oertle K.
Thalmann A.
Servi S.
Helv. Chim.
Acta
1975,
58:
2036
19b
Schmidt U.
Gombos J.
Haslinger E.
Zak H.
Chem. Ber.
1976,
109:
2628
19c
Bartlett PA.
Meadows JD.
Ottow E.
J. Am. Chem. Soc.
1984,
106:
5304
19d
Lee JY.
Kim BH.
Tetrahedron
1996,
52:
571
20
Fleming I.
Ghosh SK.
J. Chem. Soc., Perkin
Trans. 1
1998,
2733
21
Smith WC.
Xiang L.
Shen B.
Antimicrob.
Agents Chemother.
2000,
44:
1809
22
Ashton PR.
Cantrill SJ.
Gattuso G.
Menzer S.
Nepogodiev SA.
Shipway AN.
Stoddart JF.
Williams DJ.
Chem.-Eur.
J.
1997,
3:
1299
23
Whitlock CR.
Cava MP.
Tetrahedron Lett.
1994,
35:
371
24
Williams RM.
Armstrong RW.
Maruyama LK.
Dung J.-S.
Anderson OP.
J. Am. Chem. Soc.
1985,
107:
3246
25 Anstiss, M.; Nelson, A. unpublished observations, 2003 .
26
Spivey AC.
Andrews BI.
Brown AD.
Frampton CS.
Chem.
Commun.
1999,
2523
27
Hoffmann RW.
Angew.
Chem. Int. Ed.
2003,
42:
1096
28 W.C. Corporation, US patent 3067201, 1955 .
29a
Holland JM.
Lewis M.
Nelson A.
Angew. Chem. Int. Ed.
2001,
40:
4082
29b
Holland JM.
Lewis M.
Nelson A.
J.
Org. Chem.
2003,
68:
747
30
Lebsack AD.
Link JT.
Overman LE.
Stearns BA.
J.
Am. Chem. Soc.
2002,
124:
9008
31
Overman LE.
Larrow JF.
Stearns BA.
Vance JM.
Angew.
Chem. Int. Ed.
2000,
39:
213
32a
Dodds DR.
Jones JB.
J.
Am. Chem. Soc.
1988,
110:
577
32b
Baumann P.
Prelog V.
Helv. Chim. Acta
1958,
1:
2379
33
Böhm C.
Austin WF.
Trauner D.
Tetrahedron: Asymmetry
2003,
14:
71
34
Ovitt TM.
Coates GW.
J. Am. Chem. Soc.
1999,
121:
4072