| Project/Area Number |
15205013
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (A)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | HOKKAIDO UNIVERSITY |
|---|
Principal Investigator |
MIYAURA Norio Hokkaido Univ., Grad. School of Eng., Prof., 大学院工学研究科, 教授 (10002049)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
ISHIYAMA Tatsuo Hokkaido Univ., Grad. School of Eng., Asso.Prof., 大学院工学研究科, 助教授 (00232348)
YAMAMOTO Yasunori Hokkaido Univ., Grad. School of Eng., Inst., 大学院工学研究科, 助手 (30271646)
|
|---|
| Project Period (FY) |
2003 – 2006
|
| Project Status |
Completed (Fiscal Year 2006)
|
| Budget Amount *help |
¥48,360,000 (Direct Cost: ¥37,200,000、Indirect Cost: ¥11,160,000)
Fiscal Year 2006: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2005: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000)
Fiscal Year 2004: ¥8,060,000 (Direct Cost: ¥6,200,000、Indirect Cost: ¥1,860,000)
Fiscal Year 2003: ¥27,820,000 (Direct Cost: ¥21,400,000、Indirect Cost: ¥6,420,000)
|
|---|
| Keywords | Catalytic C・H Borylation / Catalytic Hydroboration / Grignard Type Addition / Organoboron Compounds / Catalytic Allylboration / Rhodium catalyst / Iridium Catalyst / Chiral Lewis Acid Catalyst |
|---|
| Research Abstract |
1. Catalytic C-H Borylation
Direct C-H borylation of arenes catalyzed by a transition metal complex was studied as an economical protocol for the synthesis of a variety of arylboron derivatives. Ir-catalyzed C-H borylation of arenes, heteroarenes, and benzylic positions of alkylarenes by bis(pinacolato)diboron or pinacolborane furnished aryl-, heteroaryl-, and benzylboron compounds.
2. Catalytic Hydroboration
Hydroboration of terminal and internal alkenes with pinacolborane or N, N', N"-trimethyl-and N, N', N"-triethylborazine was carried out at 25-50℃ in the presence of rhodium(I) or iridium(I) catalyst.
Addition of dppb or DPEphos to RhH(COXPPh_3)_3 gave the best catalyst for hydroboration of ethylene at 50℃, resulting in a quantitative yield of B, B', B"-triethyl-N, N', W-trimethylborazine. On the other hand, a complex prepared from (t-Bu)_3P and [Rh(coe)_2Cl]_2 gave the best yield for hydroboration of terminal or internal alkenes.
3, 5, 6. Rhodium and Palladium Catalyzed Addition Reactions of Organoboron compounds.
An enantioselective synthesis of cyclic and acyclic P-aryl ketones and esters via palladium(II)-or rhodium(I)-catalyzed 1,4-addition of Ar-[m] (m=B(OH)_2, BF_3K, Si(OMe)_3, SiF_3, BiAr_2) to α, β-unsaturated ketones or esters is described. The enantioselection mechanism and efficiency of a chiraphos ligand for structurally planar α, β-unsaturated ketones are discussed on the basis of the X-ray structure of the catalyst and results of DFT computational studies on the modes of coordination of the substrates to the phenylrhodium(I)/(S, S)-chiraphos intermediate.
4. Catalytric Allylboration
The asymmetric cross-coupling reaction of [CH_3CH=CHCH_2BF_3]K with aryl or 1-alkenyl bromides selectively occurred at the γ-carbon of 2-butenylborane moiety with regioselectivities in a range of 84-99%. The enantioselectivities were in a range of 77-90%ee when a palladium/CyPF-t-Bu complex was used at 80℃ in the presence of K_2CO_3 in H_2O-MeOH (9/1).
|
