Palladium‐Catalyzed Stereoselective Intramolecular Oxidative Amidation of Alkenes in the Synthesis of 1,3‐ and 1,4‐Amino Alcohols and 1,3‐Diamines

Malkov, Andrei V.; Lee, Darren S.; Barłóg, Maciej; Elsegood, Mark R. J.; Kočovský, Pavel

doi:10.1002/chem.201400123

Cited by 22 publications

(9 citation statements)

References 96 publications

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“…N , N -Dimethylformamide (DMF) was dried over CaH 2 and distilled before use. 2-Methyl- N -tosylaziridine (TsMAz), 2-methyl- N -mesylaziridine (MsMAz), and 2-phenyl- N -tosylaziridine (TsPhAz) were prepared according to reported procedures. The random copolymer P(St- co - t BMA) was prepared according to typical nitroxide-mediated polymerization (NMP) procedures .…”

Section: Methodsmentioning

confidence: 99%

Carboxylic Acid Initiated Organocatalytic Ring-Opening Polymerization of N-Sulfonyl Aziridines: An Easy Access to Well-Controlled Polyaziridine-Based Architectural and Functionalized Polymers

et al. 2019

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A highly easy and efficient metal-free methodology for the synthesis of polyaziridine-based polymers with controlled architectures and desired functionalities was developed by organocatalytic ring-opening polymerization (ROP) of N-sulfonyl aziridines with a carboxylic acid as initiator. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (MTBD) and phosphazene t-Bu-P4 organocatalysts have demonstrated high catalytic efficiency in connection with the controlled/living character of the ROP of 2-methyl-N-tosylaziridines (TsMAz) initiated by benzoic acid. Aryl carboxylic acids bearing an azido or a hydroxyl group as well as bio-derived vanillic acid and syringic acid and alkyl- and alkenyl-substituted carboxylic acids, such as acetic acid, palmitic acid, and methacrylic acid, can all initiate the ROP of TsMAz toward well-defined P(TsMAz)s. α,ω-Diamino telechelic, star-shaped P(TsMAz)s, and poly(styrene-co-methacrylic acid)-graft-poly(2-methyl-N-tosylaziridine) [P(St-co-MAA)-g-P(TsMAz)] have been conveniently synthesized from the corresponding multicarboxyl (macro)initiators. Finally, this protocol has been applied for the synthesis of a linear photoresponsive P(TsMAz) and an aggregation-induced emission (AIE)-active 4-arm P(TsMAz) star from the corresponding functionalized carboxylic acids.

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Section: Methodsmentioning

confidence: 99%

Carboxylic Acid Initiated Organocatalytic Ring-Opening Polymerization of N-Sulfonyl Aziridines: An Easy Access to Well-Controlled Polyaziridine-Based Architectural and Functionalized Polymers

et al. 2019

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“…[ 58 ] In accord with the previous observations (vide supra), the hydroxylamine derivative 133 afforded the cis -configured isoxazolidine 134 (≥30:1 dr), whereas its hydrazine analogue 135 produced the trans -configured pyrrazolidine derivative 136 (≥30:1 dr). [ 58a ] The latter products can be regarded as surrogates of 1,3-amino alcohols and diamines, respectively.…”

Section: Intramolecular Amidopalladationmentioning

confidence: 99%

The syn/anti‐Dichotomy in the Palladium‐Catalyzed Addition of Nucleophiles to Alkenes

Kočovský

Bäckvall

2014

Chemistry A European J

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114

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In this review the stereochemistry of palladium-catalyzed addition of nucleophiles to alkenes is discussed, and examples of these reactions in organic synthesis are given. Most of the reactions discussed involve oxygen and nitrogen nucleophiles; the Wacker oxidation of ethylene has been reviewed in detail. An anti-hydroxypalladation in the Wacker oxidation has strong support from both experimental and computational studies. From the reviewed material it is clear that anti-addition of oxygen and nitrogen nucleophiles is strongly favored in intermolecular addition to olefin–palladium complexes even if the nucleophile is coordinated to the metal. On the other hand, syn-addition is common in the case of intramolecular oxy- and amidopalladation as a result of the initial coordination of the internal nucleophile to the metal.

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“…Li et al reported that an 86% yield of DMBF is achieved at 25 °C and 1 atm of O 2 using trifluoroacetic acid (TFA) as the Pd(II) ligand . In this reaction, the use of dimethyl sulfoxide (DMSO) solvent has been proven to facilitate the aerobic oxidation on Pd catalysts, due to the DMSO’s ability to also act as an ancillary ligand for Pd. − Despite the high catalytic performances obtained from Pd catalysts under mild reaction conditions, the reaction was very slow; site-time-yield (STY) for DMBF formation was ∼0.35 h –1 . We studied the homocoupling reaction of MF to DMBF at 25 °C under 1 bar of O 2 pressure, and DMBF yields of 50–60% were produced with ∼100% DMBF selectivity; however, 1 week was required to achieve the results (STY = 0.09 h –1 ). − Thus, improvement of the DMBF production rate is still an important goal.…”

Section: Introductionmentioning

confidence: 99%

Selective Synthesis of 4,4′-Dimethylbiphenyl from 2-Methylfuran

Cho

Kuo

et al. 2021

ACS Sustainable Chem. Eng.

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4,4′-Dimethylbiphenyl (DMBP) is a promising platform chemical for the production of polymer precursors, plasticizers, and metal–organic frameworks among other materials. We report a two-step process to produce DMBP from 2-methylfuran (MF) via the formation of the intermediate 5,5′-dimethyl-2,2′-bifuran (DMBF). DMBF is generated from the Pd-catalyzed oxidative coupling of MF in the presence of trifluoroacetic acid (TFA) with high selectivity (94%). Optimization of reaction conditions yields a 20-fold increase in site-time-yield (STY = 6.99 h–1) compared with a previously reported protocol. High O2 pressure (7 bar) and a high TFA concentration (3 M) are critical to improve the DMBF formation rate. For the conversion of DMBF to DMBP, we show that phosphoric acid supported on silica (P-SiO2) catalyzes tandem Diels–Alder and dehydration reactions of DMBF with ethylene to produce DMBP (83% yield). The high yield and selectivity are a consequence of the weak Brønsted acid sites in P-SiO2 that dehydrate furan-ethylene cycloadducts without substantial formation of carbon deposits.

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Palladium‐Catalyzed Stereoselective Intramolecular Oxidative Amidation of Alkenes in the Synthesis of 1,3‐ and 1,4‐Amino Alcohols and 1,3‐Diamines

Cited by 22 publications

References 96 publications

Carboxylic Acid Initiated Organocatalytic Ring-Opening Polymerization of N-Sulfonyl Aziridines: An Easy Access to Well-Controlled Polyaziridine-Based Architectural and Functionalized Polymers

Carboxylic Acid Initiated Organocatalytic Ring-Opening Polymerization of N-Sulfonyl Aziridines: An Easy Access to Well-Controlled Polyaziridine-Based Architectural and Functionalized Polymers

The syn/anti‐Dichotomy in the Palladium‐Catalyzed Addition of Nucleophiles to Alkenes

Selective Synthesis of 4,4′-Dimethylbiphenyl from 2-Methylfuran

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