Abstract
A diammonium salt of chiral 1,1′-binaphthyl-2,2′-diamine (2a) and trifluoromethanesulfonimide (Tf2NH) shows excellent catalytic activity and enantioselectivity for the Diels-Alder reaction of α-acyloxyacroleins. For example, in the presence of 5 mol% of 2a and 9.5 mol% of Tf2NH, the Diels-Alder reaction of α- (cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at -75 °C to give the adducts in 88% yield with 92% exo and 91 % ee. The electron-donating property of the acyl group of the α-acyloxyacroleins increases the enantioselectivity due to the formation of strong intramolecular hydrogen bonding of the acyl group with a proton of the ammonium group in the transition state. This catalyst can be easily prepared in situ by mixing the commercially available chiral diamine and Tf2NH.
| Original language | English |
|---|---|
| Pages (from-to) | 2457-2465 |
| Number of pages | 9 |
| Journal | Advanced Synthesis and Catalysis |
| Volume | 348 |
| Issue number | 16-17 |
| DOIs | |
| Publication status | Published - Nov 2006 |
| Externally published | Yes |
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Keywords
- α-acyloxyacrolein
- 1,1′-binaphthyl-2,2′- diamine
- Ammonium salts
- Cycloaddition
- Diels-Alder reaction
ASJC Scopus subject areas
- Chemistry (miscellaneous)
- Organic Chemistry
- Catalysis
Cite this
Enantioselective Diels-Alder reaction of α-Acyloxyacroleins catalyzed by chiral 1,1′-binaphthyl-2,2′-diammonium salts. / Sakakura, Akira; Suzuki, Kenji; Ishihara, Kazuaki.
In: Advanced Synthesis and Catalysis, Vol. 348, No. 16-17, 11.2006, p. 2457-2465.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Enantioselective Diels-Alder reaction of α-Acyloxyacroleins catalyzed by chiral 1,1′-binaphthyl-2,2′-diammonium salts
AU - Sakakura, Akira
AU - Suzuki, Kenji
AU - Ishihara, Kazuaki
PY - 2006/11
Y1 - 2006/11
N2 - A diammonium salt of chiral 1,1′-binaphthyl-2,2′-diamine (2a) and trifluoromethanesulfonimide (Tf2NH) shows excellent catalytic activity and enantioselectivity for the Diels-Alder reaction of α-acyloxyacroleins. For example, in the presence of 5 mol% of 2a and 9.5 mol% of Tf2NH, the Diels-Alder reaction of α- (cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at -75 °C to give the adducts in 88% yield with 92% exo and 91 % ee. The electron-donating property of the acyl group of the α-acyloxyacroleins increases the enantioselectivity due to the formation of strong intramolecular hydrogen bonding of the acyl group with a proton of the ammonium group in the transition state. This catalyst can be easily prepared in situ by mixing the commercially available chiral diamine and Tf2NH.
AB - A diammonium salt of chiral 1,1′-binaphthyl-2,2′-diamine (2a) and trifluoromethanesulfonimide (Tf2NH) shows excellent catalytic activity and enantioselectivity for the Diels-Alder reaction of α-acyloxyacroleins. For example, in the presence of 5 mol% of 2a and 9.5 mol% of Tf2NH, the Diels-Alder reaction of α- (cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at -75 °C to give the adducts in 88% yield with 92% exo and 91 % ee. The electron-donating property of the acyl group of the α-acyloxyacroleins increases the enantioselectivity due to the formation of strong intramolecular hydrogen bonding of the acyl group with a proton of the ammonium group in the transition state. This catalyst can be easily prepared in situ by mixing the commercially available chiral diamine and Tf2NH.
KW - α-acyloxyacrolein
KW - 1,1′-binaphthyl-2,2′- diamine
KW - Ammonium salts
KW - Cycloaddition
KW - Diels-Alder reaction
UR - http://www.scopus.com/inward/record.url?scp=33845274327&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33845274327&partnerID=8YFLogxK
U2 - 10.1002/adsc.200600322
DO - 10.1002/adsc.200600322
M3 - Article
AN - SCOPUS:33845274327
VL - 348
SP - 2457
EP - 2465
JO - Advanced Synthesis and Catalysis
JF - Advanced Synthesis and Catalysis
SN - 1615-4150
IS - 16-17
ER -