Abstract
A cinchona-alkaloid-derived chiral primary-amine-catalyzed enantioselective method for the synthesis of the thermodynamically less stable indanedione-fused 2,6-trans-disubstituted spirocyclohexanones is demonstrated. Both the enantiomeric forms of the trans isomer are obtained in excellent yields and enantioselectivities. Furthermore, one of the enantiopure trans-spiranes bearing an additional α-substitution on the cyclohexanone ring was then epimerized into its thermodynamically stable cis counterpart, with little loss of enantioselectivity to demonstrate the feasibility of such a transformation. Mechanistic investigations revealed two competing pathways, a concerted Diels-Alder reaction and a stepwise Michael addition, for the formation of corresponding products.
| Original language | English |
|---|---|
| Pages (from-to) | 2420-2431 |
| Number of pages | 12 |
| Journal | Journal of Organic Chemistry |
| Volume | 81 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - 2016 Mar 18 |
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ASJC Scopus subject areas
- Organic Chemistry
Cite this
Expanding the Scope of Primary Amine Catalysis : Stereoselective Synthesis of Indanedione-Fused 2,6-Disubstituted trans-Spirocyclohexanones. / Madhusudhan Reddy, G.; Ko, Chi Ting; Hsieh, Kai Hong; Lee, Chia Jui; Das, Utpal; Lin, Wenwei.
In: Journal of Organic Chemistry, Vol. 81, No. 6, 18.03.2016, p. 2420-2431.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Expanding the Scope of Primary Amine Catalysis
T2 - Stereoselective Synthesis of Indanedione-Fused 2,6-Disubstituted trans-Spirocyclohexanones
AU - Madhusudhan Reddy, G.
AU - Ko, Chi Ting
AU - Hsieh, Kai Hong
AU - Lee, Chia Jui
AU - Das, Utpal
AU - Lin, Wenwei
PY - 2016/3/18
Y1 - 2016/3/18
N2 - A cinchona-alkaloid-derived chiral primary-amine-catalyzed enantioselective method for the synthesis of the thermodynamically less stable indanedione-fused 2,6-trans-disubstituted spirocyclohexanones is demonstrated. Both the enantiomeric forms of the trans isomer are obtained in excellent yields and enantioselectivities. Furthermore, one of the enantiopure trans-spiranes bearing an additional α-substitution on the cyclohexanone ring was then epimerized into its thermodynamically stable cis counterpart, with little loss of enantioselectivity to demonstrate the feasibility of such a transformation. Mechanistic investigations revealed two competing pathways, a concerted Diels-Alder reaction and a stepwise Michael addition, for the formation of corresponding products.
AB - A cinchona-alkaloid-derived chiral primary-amine-catalyzed enantioselective method for the synthesis of the thermodynamically less stable indanedione-fused 2,6-trans-disubstituted spirocyclohexanones is demonstrated. Both the enantiomeric forms of the trans isomer are obtained in excellent yields and enantioselectivities. Furthermore, one of the enantiopure trans-spiranes bearing an additional α-substitution on the cyclohexanone ring was then epimerized into its thermodynamically stable cis counterpart, with little loss of enantioselectivity to demonstrate the feasibility of such a transformation. Mechanistic investigations revealed two competing pathways, a concerted Diels-Alder reaction and a stepwise Michael addition, for the formation of corresponding products.
UR - http://www.scopus.com/inward/record.url?scp=84961615768&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84961615768&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.5b02921
DO - 10.1021/acs.joc.5b02921
M3 - Article
AN - SCOPUS:84961615768
VL - 81
SP - 2420
EP - 2431
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 6
ER -