Topics Archives
[Practical Example]▶ The Metallophotoredox Reaction Using a Capsule Reagent
TCI Practical Example에서는 TCI의 합성 담당 연구원이 직접 겪은 반응 사례를 분석 자료와 함께 소개하고 있습니다.
[20240205]
"metallophotoredox C-N cross-coupling reaction of 5-bromopyrimidine and morpholine using the capsule reagent"
Used Chemicals
- 5-Bromopyrimidine [B2229]
- Morpholine [M0465]
- Reagents for Metallophotoredox Cross-Coupling Reactions (HPMC encapsulated) (NiBr2(dme), [Ir[dF(CF3)ppy]2(dtbbpy)]PF6, DABCO) [R0273]
- N,N-Dimethylacetamide (= DMAc)
Procedure
Reagents for metallophotoredox cross-coupling reactions (HPMC encapsulated) (one capsule) was added to a solution of 5-bromopyrimidine (95 mg, 0.60 mmol) and morpholine (78 μL, 0.90 mmol, 1.5 eq.) in DMAc (6 mL) at room temperature. The solution was placed at a distance of 3-5 cm from Blue LED lamp and stirred for 24 hours at 60 °C. The reaction mixture was then filtered through Celite®. The filtrate was diluted with saturated Na2SO4 aq. (15 mL) and extracted with ethyl acetate (15 mL x 5). The organic layer was dried over sodium sulfate, concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane:methanol = 10:1) to afford 4-(pyrimidin-5-yl)morpholine (84 mg, 85% yield) as a pale brown solid.
Experimenter’s Comments
The reaction mixture was monitored by GC.
Irradiation of visible light was performed with Kessil A160WE Tuna Blue 40W x 2.
DMAc was degassed with nitrogen gas for 30 minutes before use.
The shape of the capsule is like below image and each capsule includes NiBr2(dme) (ca. 0.03 mmol), [Ir[dF(CF3)ppy]2(dtbbpy)]PF6 (ca. 0.12 μmol), and DABCO (ca. 1.1 mmol).
The material of the capsule is water-soluble HPMC (hydroxypropyl methylcellulose).
Analytical Data
4-(Pyrimidin-5-yl)morpholine
1H NMR (400 MHz, CDCl3); δ 8.74 (s, 1H), 8.37 (s, 2H), 3.91-3.88 (m, 4H), 3.25-3.22 (m, 4H).
Lead Reference
- Reagent and Catalyst Capsules: A Chemical Delivery System for Reaction Screening and Parallel Synthesis
Other Reference
- HPMC: A Biomass-Based Semisynthetic Sustainable Additive Enabling Clean and Fast Chemistry in Water
첨부파일 | 선택된 파일 없음 |
---|