Rhodium‐Catalyzed Synthesis of 4‐Bromo‐1,2‐dihydroisoquinolines: Access to Bromonium Ylides by the Intramolecular Reaction of a Benzyl Bromide and an α‐Imino Carbene

He, Jiang; Shi, Yinping; Cheng, Wanli; Man, Zengming; Yang, Dongdong; Li, Chuan‐Ying

doi:10.1002/anie.201512015

Cited by 96 publications

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References 114 publications

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“…1,132.5,130.4,129.2 (q,129.0,128.6,128.3,126.0,125.4 (q,4 JC-F = 3.9 Hz), 124.7, 124.2 (q, 1 JC-F = 272.0 Hz), 123. 5, 115.6, 110.5, 71.7, 35.1, 22.5, 22. = 2979, 1621, 1593, 1504, 1325, 1263, 1120, 1068, 850, 752 6,144.8,133.2,132.3,129.2,129.1,128.5,128.1,127.8,127.8 (d,124.6,123.7,115.7,115.5,115.3,111.0,71.7,35.1,22.5,22. = 2977, 2925, 1513, 1503, 1260, 1242, 1108, 841, 748 cm -1 . [α]D 20 : +92.7…”

Section: -mentioning

confidence: 99%

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Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

2020

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General Methods Experimental Procedures, Reagents and Glassware All commercially available chemicals were used as purchased for the synthesis of substrates. All reactions were carried out under an atmosphere of nitrogen in oven-dried glassware with magnetic stirring, unless otherwise indicated. Acetonitrile (MeCN) was dried over CaH2, distilled and stored inside the N2-filled glovebox. Toluene, THF and dichloromethane were purified by the Innovative Technology Solvent Delivery System. Chemicals were used as obtained from the suppliers unless otherwise stated. Solvent compositions are given in (v/v). Chromatography Flash chromatography was performed with Silicycle silica gel 60 (0.040-0.063 μm grade). Analytical thin-layer chromatography was performed with commercial glass plates coated with 0.25 mm silica gel (E. Merck, Kieselgel 60 F254). Compounds were visualized under UV-light at 254 nm and oxidized in standard KMnO4 dye followed by heating if necessary. NMR Spectroscopy Proton nuclear magnetic resonance (1 H NMR) data were acquired at 400 MHz on a Bruker AVANCEIII-400 spectrometer or at 600 MHz on a Bruker DRX-600 spectrometer. Chemical shifts (δ) are reported in parts per million (ppm) relative to residual chloroform (s, 7.26 ppm) or residual acetone (2.05 ppm). Proton decoupled Carbon-13 nuclear magnetic resonance (13 C NMR) data were acquired at 101 MHz or 126 MHz on a Bruker AVANCEIII-400. Chemical shifts are reported in ppm relative to residual chloroform (77.16 ppm) or residual acetone (29.84 ppm, 206.26 ppm). Proton decoupled Fluorine-19 nuclear magnetic resonance (19 F{ 1 H} NMR) were acquired at 377 MHz on a Bruker AV400 spectrometer. Proton decoupled Phosphorus-31 nuclear magnetic resonance (31P{1H} NMR) were acquired at 162 MHz on a Bruker AV400 spectrometer. The assignment of proton and carbon signals was assisted by COSY, HSQC, HMBC and DEPT-135 experiments where necessary. Splitting patterns are designated as s, singlet; d, doublet; t, triplet; q, quartet; p, pentet; hept, heptet; dd, doublet of doublets; dt, doublet of triplets; ddd, doublet of doublets of doublets; tt, triplet of triplets; tq, triplet of quartets; qt, quartet of triplets; m, multiplet. All NMR data were recorded at 298 K. Infrared Spectroscopy Infrared (IR) data were recorded on an Alpha-P Bruker FT-IR Spectrometer. Absorbance frequencies are reported in reciprocal centimeters (cm-1). Mass Spectrometry HRMS measurements were performed on an Agilent LC-MS TOF (Multimode: ESI + APCI + APPI). High resolution mass are given in m/z. Melting Points Melting points were measured on a Büchi B-540 and are uncorrected. Enantiomeric excesses Enantiomeric excesses were measured on an Agilent HPLC and Shimadzu HPLC. Optical rotations were measured on a Polartronic M polarimeter using a 0.5 cm cell with a Na 589 nm filter.

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confidence: 99%

“…1H-1,2,3-triazole (1m): synthesized according to reported procedure 6. 1 H NMR (400 MHz, Chloroform-d) δ 7.84 -7.76 (m, 2H),7.66 (s, 1H), 7.45 -7.33 (m, 5H), 7.35 -7.29 (m, 3H), 5.58 (s, 2H).…”

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Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

2020

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“…Triazole chemistry has been extensively studied over the last decade, in which the N-sulfuryl-1,2,3-triazoles have been used as versatile synthetic precursors for the synthesis of nitrogencontaining heterocycles. [7][8][9][10][11] We have ag reat interesti na zaheterocycles ynthesis and N-sulfonyl-1,2,3-triazoles chemistry.W e have reported ap ractical and efficient method for divergent Scheme1.Rh II catalyzedreactionf or the construction of 3,4-fusedp yrroles.…”

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“…Increasing the amount of 2a to 1.2 equivalent (entry 5-6), the overall yield of 3aa was improvedt o9 0%.H owever,r aising the temperature to 85 8Cr esulted in al ower yield (entry 7). Moreover, the use of 1,2-dichloroethane (DCE) or toluene as the solventd id not increase the yield of 3aa (entry [8][9]. The addition of Lewis acidh ave no positivee ffects (entry [10][11][12][13][14].…”

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“…Gratifyingly,w ef ound that DBU promoted the cyclization smoothly to afford 4aa in 63 %y ield 1 [c] Rh 2 (OAc) 4 CHCl 3 -75 65 2 [c] Rh 2 (oct) 4 CHCl 3 -75 82 3 [c] Rh 2 (piv) 4 CHCl 3 -75 78 4 [c] Rh 2 (S-nttl) 4 CHCl 3 -75 67 5 [d] Rh 2 (oct) 4 CHCl 3 -75 86 6Rh 2 (oct) 4 CHCl 3 -75 90 [g] 7Rh 2 (oct) 4 CHCl 3 -85 88 8Rh 2 (oct) 4 CH 2 Cl 2 -75 77 9Rh 2 (oct) 4 toluene-75 73 (entry 7). Solvent effect was then tested with DBU as the base (entry [8][9][10][11]. The results show that the nonpolar solventt oluene is the best choice.M oreover, the yield did not increase either at ah igher reaction temperature or a lower reaction temperature (entry [12][13][14].W e envisioned that the additional oxidants would promote the reaction.…”

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Rhodium(II)‐Catalyzed Reaction of 1‐Tosyl‐1,2,3‐triazoles with Morita–Baylis–Hillman Adducts: Synthesis of 3,4‐Fused Pyrroles

Jia

Jiang

Leng

et al. 2018

Chemistry An Asian Journal

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A cascade reaction of rhodium azavinylcarbenes with Morita-Baylis-Hillman (MBH) adducts enables a novel synthetic approach to 3,4-fused pyrroles. The cascade reaction begins with the insertion of O-H bond into rhodium azavinylcarbenes, subsquent sigmatropic rearrangement provides substituted α,β-unsaturated cyclic ketone intermediates. Then the intramolecular aza Michael addition/oxidative aromatization sequence give rise to a wide range of 3,4-fused pyrroles in good yields, and with excellent functional group compatibility.

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Molecular Rearrangements

Coxon¹

2020

Organic Reaction Mechanisms · 2016

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Rhodium‐Catalyzed Synthesis of 4‐Bromo‐1,2‐dihydroisoquinolines: Access to Bromonium Ylides by the Intramolecular Reaction of a Benzyl Bromide and an α‐Imino Carbene

Cited by 96 publications

References 114 publications

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

Rhodium(II)‐Catalyzed Reaction of 1‐Tosyl‐1,2,3‐triazoles with Morita–Baylis–Hillman Adducts: Synthesis of 3,4‐Fused Pyrroles

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