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Julianna M. Mouat ; Jonas K. Widness ; Daniel G. Enny , et al. ACS Catal.,2023,13(13):9018-9024. DOI: 10.1021/acscatal.3c01984 PubMed ID: 38283073
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Abstract: Semiconductor quantum dots (QDs) offer many advantages as photocatalysts for synthetic photoredox catalysis, but no reports have explored the use of QDs with nickel catalysts for C–C bond formation. We show here that 5.7 nm CdS QDs are robust photocatalysts for photoredox-promoted cross-electrophile coupling (turnover number (TON) up to 40,000). These conditions can be utilized on a small scale (96-well plate) or adapted to flow. NMR studies show that triethanolamine (TEOA)-capped QDs are the active catalyst and that TEOA can displace native phosphonate and carboxylate ligands, demonstrating the importance of the QD surface chemistry.
Keywords: quantum dot ; nanoplatelet ; nickel ; cross-electrophile coupling ; C?C bond formation ; photochemistry
Purchased from AmBeed: 83948-53-2 ; 180695-79-8 ; 166953-64-6 ; 131379-33-4 ; 364359-05-7
CAS No. : | 83948-53-2 | MDL No. : | MFCD02683429 |
Formula : | C8H16BrNO2 | Boiling Point : | - |
Linear Structure Formula : | (CH3)3COC(O)NH(CH2)3Br | InChI Key : | IOKGWQZQCNXXLD-UHFFFAOYSA-N |
M.W : | 238.12 | Pubchem ID : | 4460490 |
Synonyms : |
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Chemical Name : | tert-Butyl N-(3-Bromopropyl)carbamate |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312+P330-P302+P352-P304+P340+P312-P305+P351+P338-P332+P313-P337+P313-P403+P233-P405-P501 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In N,N-dimethyl-formamide; at 70℃; for 15h; | The diethyl ester of chelidamic acid (Scrimin, P.; Tecilla, P.; Tonellato, U.; Vendrame, T. J. Org. Chem. 1989, 54, 5988) (150mg) was dissolved in dry dimethylformamide (2 mL). 3-(tert-Butoxy-amino)-propyl bromide (164 mg) and potassium carbonate (130 mg) were added. The resulting mixture was stirred for 15h at 70C. The reaction was quenched with a saturated ammonium chloride aqueous solution and then washed into separatory funnel using ethyl acetate. The layers were separated, and the aqueous layer was extracted 3 times with ethyl acetate. The combined organic solutions were dried over magnesium sulfate, and concentrated in vacuo to a residue. The residue was purified by silica gel chromatography (Merck SuperVarioFlash 30g column, Si60 15-40mum), using gradient elution with a mixture of heptane (A) and ethyl acetate (B) (gradient : 60% A : 40% B up to 50% A : 50% B) to give 4-(3-tert-butoxycarbonylamino-propoxy)-pyridine-2,6-dicarboxylic acid diethyl ester (150 mg) : Cl (Method D) :m/z=397 MH+ 1H N.M.R. (400 MHz, DMSO-d6, delta in ppm) : 1,34 (t, J = 7,0 Hz, 6H) ; 1,36 (s, 9H) ; 1,86 (m, 2H) ; 3,10 (q, J = 6,5 Hz, 2H) ; 4,21 (t, J = 6,5 Hz, 2H) ; 4,37 (q, J = 7,0 Hz, 4H) ; 6,89 (m broad, 1 H) ; 7,71 (s, 2H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With potassium carbonate; potassium iodide; In N,N-dimethyl-formamide; at 120℃; for 6.0h; | [00347] Synthesis of tert-butyl 3-(3-bromo-5-(trifluoromethyl)phenoxy)propylcarbamate (10): 3-Bromo-5-(trifluoromethyl)phenol (2 g, 8.4 mmol) was dissolved in 35 mL of DMF. tert-Butyl 3-bromopropylcarbamate (2.03 g, 8.4 mmol), K2CO3 (3.49 g, 25.2 mmol) and KI (2.7 g, 16.8 mmol) were added. The reaction was stirred at 120 C for 6 h. After cooling to room temperature, the mixture was poured into 35 mL of H20 and extracted with EtO Ac (50 mL X 3). The combined organic solvents were dried over anhydrous Na2S04, concentrated and purified by silica gel chromatography (40-80% EtO Ac/petroleum ether) to give 1.5 g of tert-butyl 3-(3-bromo-5-(trifluoromethyl)phenoxy)propylcarbamate (10). Yield: 45%. LCMS: m/z 344.1 [M-55]+; tR = 2.35 min. |
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