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Review
. 2013 Aug 15:9:1677-95.
doi: 10.3762/bjoc.9.192.

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

Ping-An Wang  1
Affiliations
Review

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

Ping-An Wang. Beilstein J Org Chem. .

Abstract

Enantioselective desymmetrization of meso-aziridines and meso-epoxides with various nucleophiles by organocatalysis has emerged as a cutting-edge approach in recent years. This review summarizes the origin and recent developments of enantioselective desymmetrization of meso-aziridines and meso-epoxides in the presence of organocatalysts.

Keywords: aziridine; desymmetrization; enantioselectivity; epoxide; organocatalysis.

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Figures

Figure 1
Figure 1
The catalyzed enantioselective desymmetrization.
Figure 2
Figure 2
Cinchona alkaloid-derived catalysts OC-1 to OC-11.
Scheme 1
Scheme 1
The enantioselective desymmetrization of meso-aziridines in the presence of selected Cinchona alkaloid-derived catalysts.
Figure 3
Figure 3
Cinchona alkaloid-derived catalysts OC-12 to OC-19.
Scheme 2
Scheme 2
The enantioselective ring-opening of aziridines in the presence of OC-16.
Scheme 3
Scheme 3
OC-16 catalyzed enantioselective ring-opening of aziridines.
Figure 4
Figure 4
The chiral phosphoric acids catalysts OC-20 and OC-21.
Scheme 4
Scheme 4
OC-20 and OC-21 catalyzed enantioselective desymmetrization of meso-aziridines.
Figure 5
Figure 5
The proposed mechanism for chiral phosphorous acid-induced enantioselctive desymmetrization of meso-aziridines (chiral PA = OC-21).
Scheme 5
Scheme 5
OC-21 catalyzed enantioselective desymmetrization of meso-aziridines by Me3SiSPh.
Scheme 6
Scheme 6
OC-21 catalyzed the enantioselective desymmetrization of meso-aziridines by Me3SiSePh/PhSeH.
Figure 6
Figure 6
L-Proline and its derivatives OC-22 to OC-27.
Scheme 7
Scheme 7
OC-23 catalyzed enantioselective desymmetrization of meso-aziridines.
Figure 7
Figure 7
Proposed bifunctional mode of action of OC-23.
Figure 8
Figure 8
The chiral thioureas OC-28 to OC-44 for the desymmetrization of meso-aziridines.
Scheme 8
Scheme 8
Desymmetrization of meso-aziridines with OC-41.
Figure 9
Figure 9
The chiral guanidines (OC-45 to OC-48).
Scheme 9
Scheme 9
OC-46 catalyzed desymmetrization of meso-aziridines by arylthiols.
Scheme 10
Scheme 10
Desymmetrization of cis-aziridine-2,3-dicarboxylate.
Figure 10
Figure 10
The proposed activation mode of OC-46.
Scheme 11
Scheme 11
The enantioselective desymmetrization of meso-aziridines by amine/CS2 in the presence of OC-46.
Figure 11
Figure 11
The chiral 1,2,3-triazolium chlorides OC-49 to OC-55.
Scheme 12
Scheme 12
The enantioselective desymmetrization of meso-aziridines by Me3SiX (X = Cl or Br) in the presence of OC-54 or OC-55.
Figure 12
Figure 12
Early organocatalysts for enantioselective desymmetrization of meso-epoxides.
Scheme 13
Scheme 13
Attempts of enantioselective desymmetrization of meso-epoxides in the presence of OC-58 or OC-60.
Scheme 14
Scheme 14
The enantioselective desymmetrization of a meso-epoxide containing one P atom.
Figure 13
Figure 13
Some chiral phosphoramide and chiral phosphine oxides.
Scheme 15
Scheme 15
OC-62 catalyzed enantioselective desymmetrization of meso-epoxides by SiCl4.
Figure 14
Figure 14
The proposed mechanism of the chiral HMPA-catalyzed desymmetrization of meso-epoxides.
Scheme 16
Scheme 16
The enantioselective desymmetrization of meso-epoxides in the presence of OC-63.
Figure 15
Figure 15
The Chiral phosphine oxides (OC-70 to OC-77) based on an allene backbone.
Scheme 17
Scheme 17
OC-73 catalyzed enantioselective desymmetrization of meso-epoxides by SiCl4.
Figure 16
Figure 16
Chiral pyridine N-oxides used in enantioselective desymmetrization of meso-epoxides.
Scheme 18
Scheme 18
Catalyzed enantioselective desymmetrization of meso-epoxides in the presence of OC-80 or OC-82.
Figure 17
Figure 17
Chiral pyridine N-oxides OC-85 to OC-94.
Scheme 19
Scheme 19
Enantioselective desymmetrization of cis-stilbene oxide by using OC-85 to OC-92 as catalysts.
Figure 18
Figure 18
A novel family of helical chiral pyridine N-oxides OC-95 to OC-97.
Scheme 20
Scheme 20
Desymmetrization of meso-epoxides catalyzed by OC-95 to OC-97.
Scheme 21
Scheme 21
OC-98 catalyzed enantioselective desymmetrization of meso-epoxides by SiCl4.
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