Synthetic Organic Chemistry based on N-Ar Axis.
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- Kondo Kazuhiro
- School of Pharmaceutical Sciences, Toho University
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- Murakami Yasuoki
- School of Pharmaceutical Sciences, Toho University
Bibliographic Information
- Other Title
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- 窒素‐アリール軸を基盤にした有機合成化学
- チッソ アリールジク オ キバン ニ シタ ユウキ ゴウセイ カガク
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Abstract
In this review, our recent studies in relation to synthetic organic chemistry based on the N-Ar axis, are embodied, which are divided by content into three sections as follows : (i) development of sufficiently chemoselective N-acylation reagents : a variety of storable N-acetyl-N- (2-trifluo-romethylphenyl) acetamide, N-benzoyl- (2-chlorophenyl) benzamide and N-acyl-N- (2, 3, 4, 5, 6-pentafluorophenyl) methanesufonamide, have been developed after systematic research on the structure-reactivity relationship and were found to serve as N-acylation reagents, exhibiting suffi-ciently better chemoselectivity compared with current N-acylation reagents; (ii) fundamental stud-ies of a chiral axis due to an acyclic imide-Ar Bond : the first example of optically active N-acyl-N- (2-t-butylphenyl) acetamide which possesses axial chirality based on an acyclic imide N-Ar bond rotation, has been found. Furthermore, the relationship between the stability to racemization and the steric and electronic effects, was elucidated; (iii) development of a chiral ligand possessing a N-Ar prochiral axis : our chiral ligand was designed on the following concept. As a chiral ligand design element for asymmetric transition metal catalyst, we use a “N-Ar prochiral axis”. Accordingly, though the N-Ar axis in our ligand is configurationally flexible, “prochiral”, the formation of the metal-our ligand complex should lead to a stable “chiral” N-Ar axis. And if this formation is largely reflected by the asymmetric center in the neighboring group, one of the two diastereomeric complexes due to the N-Ar axis, is expected to be selectively formed. Our synthesized ligands were evaluated with a standard palladium-catalyzed asymmetric allylic substitution and were found to exhibit high selectivity (up to 99% ee).
Journal
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- Journal of Synthetic Organic Chemistry, Japan
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Journal of Synthetic Organic Chemistry, Japan 59 (9), 866-878, 2001
The Society of Synthetic Organic Chemistry, Japan
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Keywords
Details 詳細情報について
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- CRID
- 1390001205277477376
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- NII Article ID
- 10012287129
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- NII Book ID
- AN0024521X
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- COI
- 1:CAS:528:DC%2BD3MXmvFShtLk%3D
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- ISSN
- 18836526
- 00379980
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- NDL BIB ID
- 5905527
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- Text Lang
- ja
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- Data Source
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- JaLC
- NDL
- Crossref
- CiNii Articles
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- Abstract License Flag
- Disallowed