2005 Fiscal Year Final Research Report Summary
Development of Allyl-Transfer Reaction and Its New Aspect
| Project/Area Number |
15350063
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | Okayama University of Science |
|---|
Principal Investigator |
NOKAMI Junzo Okayama Univ of Sci., Applied Chemistry, Prof., 工学部, 教授 (70109742)
|
|---|
| Project Period (FY) |
2003 – 2005
|
| Keywords | allyl-transfer reaction / homoallylic alcohol / asymmetric synthesis / Katsuki-Sharpless AE / [3.3]-sigmatropy / tetrahydropyran / Prins cyclization reaction / (-)-menthone |
|---|
| Research Abstract |
To date, there have been no reported methods for effectively synthesizing homoallylic alcohols (2,RCH(OH)CH_2CH=CHR^3) via alk-2-enylation of aldehydes (RCHO). On the other hand, we recently discovered the first convenient and highly stereoselective but-2-enylation of aldehydes (RCHO) to give (RC^*H(OH)CH_2CH=CHCH_3) by allyl-transfer reaction, in which γ-adduct of homoallylic alcohol (1,R^1R^2C^*(OH)C^*HR^3CH=CH_2) surved as an allyl donor and its allylic functionality (R^3CH=CHCH_2) was transfered to aldehyde due to [3.3]-sigmatropic rearrangement via the most stable 6-membered chair-like cyclic transition state of the oxocarbenium ion intermediate (RCH=O^+C^*R^1R^2C^*HR^3CH=CH_2; R^3=CH_3) derived from hemiacetal (RCH(OH)OC^*R^1R^2C^*HR^3CH=CH^2) of aldehyde and 1. Further, we demontrated the possibility of alk-2-enylation of aldehydes via an allyl-transfer reaction using optically active menthones ((-)-,(+)-, and (+)-iso) as chiral auxiliaries. We also discovered that this improved the yield of the product due to an icrease in the steric valk of the alkyl chains. Highly optically acitive 2,3,4,6-tetrasubstituted tetrahydropyrans were prepared in good yield by Prins cyclization reaction of 2 and aldehydes.
More recently, we discovered an asymmetric 4-benzyloxybut-2-enylation of aldehydes to give α-adduct of homoallylic alcohols (RC^*H(OH)CH_2CH=CHCH_2OBn), in which we successfully prepared the necessary homoallylic alcohol (R^4C^*H(HO)C^*HR^3CH=CH^2; R^3=CH_2OBn) without using organometallic compounds such as R^3CH=CHCH_2M (M=metal) which is impossible to prepare because of its intability (when R^3=CYR_2;Y=OBn, halogens).
We discovered "Allyl-Transfer reaction" which gave highly optically active and a variety of fuctionalyzed α-adduct of homoallylic alcohols, conveniently.
|
Research Products
(13 results)
-
[Journal Article] Convenient synthesis of highly optically active 2,3,4,6-tetra-substituted tetrahydropyrans via Prins cyclization reaction (PCR) of optically active homoallylic alcohols with aldehydes2006
Author(s)
Kataoka, K., Ode, Y., Matsumoto, M., Nokami, J.
-
Journal Title
Tetrahedron 62
Pages: 2471-2483
Description
「研究成果報告書概要(和文)」より
-
-
-
-
-
-
[Journal Article] Isolation and synthesis of a new natural lactone in apple juice (Malus x domestica var. Orin)2004
Author(s)
Kitaura, T., Endo, H., Nakamoto, H., Ishihara, M., Kawai, T., Nokami, J.
-
Journal Title
Flavour and Fragrance J. 19
Pages: 221-224
Description
「研究成果報告書概要(和文)」より
-
-
[Journal Article] Isolation and synthesis of a new natural lactone in apple juice(Malus x domestica var.Orin)2004
Author(s)
Kitaura, T, Endo, H., Nakamoto, H., Ishihara, M., Kawai, T., Nokami, J.
-
Journal Title
Flavour and Fragrance J. 19
Pages: 221-224
Description
「研究成果報告書概要(欧文)」より
-
-
-
-
