Efficient construction of organic molecular skeleton by using spiro-type catalysts
| Project/Area Number |
22350041
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
SASAI Hiroaki 大阪大学, 産業科学研究所, 教授 (90205831)
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| Co-Investigator(Kenkyū-buntansha) |
TAKENAKA Kazuhiro 大阪大学, 産業科学研究所, 助教 (20423113)
TAKIZAWA Shinobu 大阪大学, 産業科学研究所, 准教授 (50324851)
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| Project Period (FY) |
2010 – 2012
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| Project Status |
Completed (Fiscal Year 2012)
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| Budget Amount *help |
¥18,330,000 (Direct Cost: ¥14,100,000、Indirect Cost: ¥4,230,000)
Fiscal Year 2012: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2011: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2010: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000)
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| Keywords | 有機化学 / 合成化学 / 触媒 / キラル配位子 / 分子認識 / 不斉 / スピロ / パラジウム / 酸化 / 複素環 / 配位子 / SPRIX / チオアミド / イオン液体 / NHC / トリアゾール / Huisgen反応 / スピロビスイソオキサゾリン / Wacker型反応 / Pd(IV) / Huisen反応 / トリアゾリウム |
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| Research Abstract |
We have developed a unique chiral ligand SPRIX (1), possessing isoxazoline coordination sites on a rigid spiro backbone. The good affinity of SPRIX towards Pd(II) and its high stability under acidic and oxidative conditions encouraged us to explore new asymmetric Pd catalysis.Herein, we have developed an enantioselective oxidative sequential reaction of alkynyl cyclohexadienones 2 catalyzed by Pd-SPRIX complex, which involves an unusual carboxylation of Pd enolate intermediate. The reaction of 2 in the presence of 10 mol % of Pd(OAc)2 and 15 mol % of (M,S,S)-i-Pr-SPRIX (1d) under an oxygen atmosphere (1 atm) in a 9:1 mixture of AcOH-toluene at 60 °C proceeded smoothly to give product 3 in good yields with up to 71% ee. We have also developed a novel enantioselective Pd(II)/Pd(IV) catalysis of alkenyl alcohols utilizing 1,1-diphenylbut-3-en-1-ol (4), leading to optically active 4-acetoxy-5,5-diphenyltetrahydrofuran (5) in 92% yield with 90% ee.
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Report
(4 results)
Research Products
(72 results)
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[Book] Morita-Baylis-Hillman Reaction2012
Author(s)
Sasai, H.; Takizawa, S.
Publisher
In ComprehensiveChirality; Yamamoto, H.; Carreira, E., Eds. ELSEVIER Ltd, UK, 2012; Volume 6 (Synthetic Methods V - Organocatalysis)
Related Report
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