Abstract
Kinetic resolution of nitroallylic amines was established using chiral α,α-l-diphenylprolinol silyl ether auxiliary through isolation of the dihydrooxazine N-oxide intermediates. Further hydrolyzing the resting states provided tetrahydropyridines in high chemical yields and high to excellent stereoselectivities (up to >20:1 dr and 98% ee). A detailed mechanistic explanation for stereoselective protonation in the dihydrooxazine was probed computationally. In addition, the probable intermediates in α-halogenation of aldehydes (masked with enamines) were isolated to provide crystallographic evidence.
| Original language | English |
|---|---|
| Pages (from-to) | 3046-3049 |
| Number of pages | 4 |
| Journal | Organic Letters |
| Volume | 18 |
| Issue number | 13 |
| DOIs | |
| Publication status | Published - 2016 Jul 1 |
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ASJC Scopus subject areas
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
Cite this
Dihydrooxazine N-Oxide Intermediates as Resting States in Organocatalytic Kinetic Resolution of Functionalized Nitroallylic Amines with Aldehydes. / Gurubrahamam, Ramani; Chen, Yan Ming; Huang, Wan Yun; Chan, Yu Te; Chang, Hsiang Kai; Tsai, Ming Kang; Chen, Kwunmin.
In: Organic Letters, Vol. 18, No. 13, 01.07.2016, p. 3046-3049.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Dihydrooxazine N-Oxide Intermediates as Resting States in Organocatalytic Kinetic Resolution of Functionalized Nitroallylic Amines with Aldehydes
AU - Gurubrahamam, Ramani
AU - Chen, Yan Ming
AU - Huang, Wan Yun
AU - Chan, Yu Te
AU - Chang, Hsiang Kai
AU - Tsai, Ming Kang
AU - Chen, Kwunmin
PY - 2016/7/1
Y1 - 2016/7/1
N2 - Kinetic resolution of nitroallylic amines was established using chiral α,α-l-diphenylprolinol silyl ether auxiliary through isolation of the dihydrooxazine N-oxide intermediates. Further hydrolyzing the resting states provided tetrahydropyridines in high chemical yields and high to excellent stereoselectivities (up to >20:1 dr and 98% ee). A detailed mechanistic explanation for stereoselective protonation in the dihydrooxazine was probed computationally. In addition, the probable intermediates in α-halogenation of aldehydes (masked with enamines) were isolated to provide crystallographic evidence.
AB - Kinetic resolution of nitroallylic amines was established using chiral α,α-l-diphenylprolinol silyl ether auxiliary through isolation of the dihydrooxazine N-oxide intermediates. Further hydrolyzing the resting states provided tetrahydropyridines in high chemical yields and high to excellent stereoselectivities (up to >20:1 dr and 98% ee). A detailed mechanistic explanation for stereoselective protonation in the dihydrooxazine was probed computationally. In addition, the probable intermediates in α-halogenation of aldehydes (masked with enamines) were isolated to provide crystallographic evidence.
UR - http://www.scopus.com/inward/record.url?scp=84977279591&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84977279591&partnerID=8YFLogxK
U2 - 10.1021/acs.orglett.6b00493
DO - 10.1021/acs.orglett.6b00493
M3 - Article
AN - SCOPUS:84977279591
VL - 18
SP - 3046
EP - 3049
JO - Organic Letters
JF - Organic Letters
SN - 1523-7060
IS - 13
ER -