Abstract
The organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in the presence of an organocatalyst. The desired Michael adducts were typically obtained in high chemical yields and high to excellent stereoselectivities (up to 97 % yield, 93 % ee). An efficient desymmetrization method was developed for the synthesis of enantiomeric products by using either camphor-derived pyrrolidine V or cinchonidine-derived primary amine VII as a catalyst. The absolute stereochemistry of the (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4- methylcyclohexanone (3a) and (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4-tert- butylcyclohexanone (3b) was confirmed by single-crystal X-ray structure analyses. The direct organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in CHCl 3. The desired Michael adducts were obtained in high chemical yields and stereoselectivities (up to 97 % yield, 93 % ee). Enantiomeric products were obtained by using either a camphor-derived pyrrolidine or a cinchonidine-derived primary amine as a catalyst.
| Original language | English |
|---|---|
| Pages (from-to) | 2699-2707 |
| Number of pages | 9 |
| Journal | European Journal of Organic Chemistry |
| Issue number | 13 |
| DOIs | |
| Publication status | Published - 2013 May 1 |
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Keywords
- Asymmetric catalysis
- Enantioselectivity
- Michael addition
- Organocatalysis
- Synthetic methods
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
Cite this
Desymmetrization and switching of stereoselectivity in direct organocatalytic Michael addition of ketones to 1,1-bis(phenylsulfonyl)ethylene. / Chen, Yan Ming; Lee, Pei Hsun; Lin, Jun; Chen, Kwunmin.
In: European Journal of Organic Chemistry, No. 13, 01.05.2013, p. 2699-2707.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Desymmetrization and switching of stereoselectivity in direct organocatalytic Michael addition of ketones to 1,1-bis(phenylsulfonyl)ethylene
AU - Chen, Yan Ming
AU - Lee, Pei Hsun
AU - Lin, Jun
AU - Chen, Kwunmin
PY - 2013/5/1
Y1 - 2013/5/1
N2 - The organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in the presence of an organocatalyst. The desired Michael adducts were typically obtained in high chemical yields and high to excellent stereoselectivities (up to 97 % yield, 93 % ee). An efficient desymmetrization method was developed for the synthesis of enantiomeric products by using either camphor-derived pyrrolidine V or cinchonidine-derived primary amine VII as a catalyst. The absolute stereochemistry of the (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4- methylcyclohexanone (3a) and (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4-tert- butylcyclohexanone (3b) was confirmed by single-crystal X-ray structure analyses. The direct organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in CHCl 3. The desired Michael adducts were obtained in high chemical yields and stereoselectivities (up to 97 % yield, 93 % ee). Enantiomeric products were obtained by using either a camphor-derived pyrrolidine or a cinchonidine-derived primary amine as a catalyst.
AB - The organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in the presence of an organocatalyst. The desired Michael adducts were typically obtained in high chemical yields and high to excellent stereoselectivities (up to 97 % yield, 93 % ee). An efficient desymmetrization method was developed for the synthesis of enantiomeric products by using either camphor-derived pyrrolidine V or cinchonidine-derived primary amine VII as a catalyst. The absolute stereochemistry of the (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4- methylcyclohexanone (3a) and (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4-tert- butylcyclohexanone (3b) was confirmed by single-crystal X-ray structure analyses. The direct organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in CHCl 3. The desired Michael adducts were obtained in high chemical yields and stereoselectivities (up to 97 % yield, 93 % ee). Enantiomeric products were obtained by using either a camphor-derived pyrrolidine or a cinchonidine-derived primary amine as a catalyst.
KW - Asymmetric catalysis
KW - Enantioselectivity
KW - Michael addition
KW - Organocatalysis
KW - Synthetic methods
UR - http://www.scopus.com/inward/record.url?scp=84876525737&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84876525737&partnerID=8YFLogxK
U2 - 10.1002/ejoc.201201635
DO - 10.1002/ejoc.201201635
M3 - Article
AN - SCOPUS:84876525737
SP - 2699
EP - 2707
JO - Annalen der Pharmacie
JF - Annalen der Pharmacie
SN - 0075-4617
IS - 13
ER -