Abstract
The stereochemical features and synthetic potentials are described of the classic [1,2]-Wittig rearrangement which is now recognized to proceed via the radical cleavage-recombination mechanism. First, the [1,2]-Wittig rearrangement of enantio-defined α-benzyloxypropyllithium and its (R)-α-methylbenzyloxy analogs is shown to proceed predominantly with inversion of configuration at the Li-bearing terminus and retention of configuration at the migrating carbon. Second, the [1,2]-Wittig rearrangement of O-glycosides of both acetal and ketal types, including those derived from D-ribose and D-glucose, is demonstrated to proceed with complete retention of either the α- or β-anomeric configuration, along with efficient stereocontrol over the newly created chiral center on the side chain to afford the novel classes of stereo-defined C-glycosides in good yields.
| Original language | English |
|---|---|
| Pages (from-to) | 1000-1008 |
| Number of pages | 9 |
| Journal | Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry |
| Volume | 54 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Jan 1 1996 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Organic Chemistry
Cite this
[1,2]-Wittig rearrangement : Stereochemical features and synthetic utilities. / Tomooka, Katsuhiko; Nakai, Takeshi.
In: Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, Vol. 54, No. 11, 01.01.1996, p. 1000-1008.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - [1,2]-Wittig rearrangement
T2 - Stereochemical features and synthetic utilities
AU - Tomooka, Katsuhiko
AU - Nakai, Takeshi
PY - 1996/1/1
Y1 - 1996/1/1
N2 - The stereochemical features and synthetic potentials are described of the classic [1,2]-Wittig rearrangement which is now recognized to proceed via the radical cleavage-recombination mechanism. First, the [1,2]-Wittig rearrangement of enantio-defined α-benzyloxypropyllithium and its (R)-α-methylbenzyloxy analogs is shown to proceed predominantly with inversion of configuration at the Li-bearing terminus and retention of configuration at the migrating carbon. Second, the [1,2]-Wittig rearrangement of O-glycosides of both acetal and ketal types, including those derived from D-ribose and D-glucose, is demonstrated to proceed with complete retention of either the α- or β-anomeric configuration, along with efficient stereocontrol over the newly created chiral center on the side chain to afford the novel classes of stereo-defined C-glycosides in good yields.
AB - The stereochemical features and synthetic potentials are described of the classic [1,2]-Wittig rearrangement which is now recognized to proceed via the radical cleavage-recombination mechanism. First, the [1,2]-Wittig rearrangement of enantio-defined α-benzyloxypropyllithium and its (R)-α-methylbenzyloxy analogs is shown to proceed predominantly with inversion of configuration at the Li-bearing terminus and retention of configuration at the migrating carbon. Second, the [1,2]-Wittig rearrangement of O-glycosides of both acetal and ketal types, including those derived from D-ribose and D-glucose, is demonstrated to proceed with complete retention of either the α- or β-anomeric configuration, along with efficient stereocontrol over the newly created chiral center on the side chain to afford the novel classes of stereo-defined C-glycosides in good yields.
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UR - http://www.scopus.com/inward/citedby.url?scp=0030283604&partnerID=8YFLogxK
U2 - 10.5059/yukigoseikyokaishi.54.1000
DO - 10.5059/yukigoseikyokaishi.54.1000
M3 - Article
AN - SCOPUS:0030283604
VL - 54
SP - 1000
EP - 1008
JO - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
JF - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
SN - 0037-9980
IS - 11
ER -