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Grace Trammel ; Rositha Kuniyil ; Phillip Crook , et al. JACS,2021,143(40):16502-16511. DOI: 10.1021/jacs.1c05902 PubMed ID: 34582691
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Abstract: Indole dearomatization is an important strategy to access indolines, a motif present in a variety of natural products and pharmaceuticals. Herein, a method for transition-metal catalyzed regiodivergent dearomative arylboration of indoles to generate diverse indolines is presented. The method accomplishes intermolecular dearomatization of simple indoles through a migratory insertion pathway on substrates that lack activating or directing groups on the C2- or C3-positions. Synthetically useful C2- and C3-borylated indolines can be accessed through a simple change in N-protecting group in high regio- and diastereoselectivities (up to >50:1 rr and >20:1 dr) from readily available starting materials. Additionally, the origin of regiodivergence was explored experimentally and computationally to uncover the remarkable interplay between carbonyl orientation of the N-protecting group on indole, electronics of the C2-C3 p-bond, and sterics. The method enabled the first enantioselective synthesis of (-)-azamedicarpin.
Purchased from AmBeed: 213318-44-6
CAS No. : | 213318-44-6 | MDL No. : | MFCD02093045 |
Formula : | C13H16BNO4 | Boiling Point : | - |
Linear Structure Formula : | C8H5(NCOOC(CH3)3)B(OH)2 | InChI Key : | SVIBPSNFXYUOFT-UHFFFAOYSA-N |
M.W : | 261.08 | Pubchem ID : | 2773302 |
Synonyms : |
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Chemical Name : | N-Boc-indole-2-boronic Acid |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P233-P260-P261-P264-P270-P271-P280-P301+P312-P302+P352-P304-P304+P340-P305+P351+P338-P312-P321-P330-P332+P313-P337+P313-P340-P362-P403-P403+P233-P405-P501 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-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;tetrakis(triphenylphosphine) palladium(0); In water; acetonitrile; at 85℃; for 20h; | [l-(tert-butoxycarbonyl)-lH-indol-2-yl]boronic acid (2.22 g, 8.49 mmol), 6- chloropyrazin-2-amine (1.00 g, 7.72 mmol), K2CO3 (2.67 g, 19.3 mmol) and Pd(PPh3)4 (180 mg, 0.15 mmol) were mixed in MeCN/water (3.5: 1) and stirred at 85 0C for 20 hours. The reaction mixture was concentrated and the residue was extracted with EtOAc (2x 40 mL) and water (50 mL). The organic layers were combined, dried (Na2SO^, filtered and concentrated to give 2.5 g of a brown solid of tert-butyl 2-(6-aminopyrazin-2-yl)- lH-indole-l-carboxylate. The material was used in the next step without further purification. To tert-butyl 2-(6-aminopyrazin-2-yl)-lH-indole- l-carboxylate (1.1 g, 3.5 mmol) in dry toluene (10 mL) were added methyl 6-chloronicotinate (0.67 g, 3.90 mmol), K2CO3 (7.35 g, 53.2 mmol), (+/-)-BINAP (0.1 1 g, 0.18 mmol) and Pd(OAc)2 (40 mg, 0.18 mmol). The mixture was re fluxed for 50 minutes. The solvent was evaporated and the residue was extracted with EtOAc (2x100 mL) and washed with water/brine (1 : 1 ; 100 mL). The organic layers were combined, dried (Na2Spsi4), filtered and concentrated to give 2 g of crude product. Purification was performed by flash chromatography (1percent NEt3 in DCM-> 1percent NEt3, 1percent MeOH in DCM). This gave tert-butyl 2-(6-[5-(methoxycarbonyl)pyridin-2- yl]amino}pyrazin-2-yl)-lH-indole- l-carboxylate (620 mg). The material was divided into four microwave tubes (155 mg, 0.35 mmol in each) and dissolved in MeOH. 2M aq NaOH (0.35 mL, 0.70 mmol) was added and the reaction mixture was irradiated in a microwave oven at 1 10 0C for 15 minutes. 6M aq HCl (0.12 mL, 0.70 mmol) was added. The reactions were combined and concen- trated in vacuo to give the crude title compound as a brown solid (720 mg). MS (ESI+) for C18H 13N5O2 m/z 332 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 95℃; for 10h; | FIG. 1 shows a synthesis reaction formula of an indolylbenzothiadiazole derivative according to Examples. N-Boc-indole-2-boronic acid (1 mmol) represented by the formula (4)4-bromo-2, 1, 3-benzothiadiazole (1 mmol) and Pd (PPh 3) 4 (0.1 mmol) represented by the formula (5)The reaction was carried out in dioxane / 2 M aqueous solution of K 2 CO 3 at 95 ° C. for 10 hours. Incidentally,"Boc" represents a tert-butoxycarbonyl group as shown by the formula (6).Next, after post-treatment according to a conventional method, purification was carried out by silica gel column chromatography to obtain a fluorescent organic dye as an indolylbenzothiadiazole derivative represented by the formula (7) in a yield of 83percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate; In water; N,N-dimethyl-formamide; at 60℃; for 4h; | A mixture of compound 1 (118 mg, 0.5 mmol), (1-(tert-butoxycarbonyl)-1H-indol-2-yl)boronic acid (130 mg, 0.5 mmol), aq. K3PO4 (1 M, 1.5 mmol) and Pd(dppf)Cl2 (37 mg, 0.05 mmol) in DMF (5 mL) was stirred at 60 C for 4 h. The reaction mixture was diluted with H2O and extracted with EA. The organic layer was washed with H2O, brine, dried over Na2SO4. After concentrated, the residue was purified by prep-TLC (PE : EA = 5:1) to give the product of compound 2 (100 mg, yield: 54 %). 1H NMR (CDCl3, 400 MHz) delta 8.77 (s, 1H), 8.58 (d, J = 4.4Hz, 1H), 8.30 (d, J = 8.4Hz, 1H), 7.60 (d, J = 7.6Hz, 1H), 7.25~7.41 (m, 3H), 6.58 (s, 1H), 1.33 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A 1 dram vial was charged with aryl bromide (122 mg, 0.5 mmol), aryl boronic acid (196 mg, 0.75 mmol) and K3PO4 (172 mg, 0.75 mmol). 2 wt % TPGS is added to the vial (1 mL) and the mixture is set to stir for about 5 min. The catalyst solution is added to the reaction mixture (0.25 mL, 0.5 mol % Pd) and the reaction vessel is purged with argon, sealed with Teflon and set to stir for 1.5 hrs at 45 C. |
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