2016
DOI: 10.1002/celc.201600519
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Electrochemical Properties and Reactions of Oxygen‐Containing Organotrifluoroborates and Their Boronic Acid Esters

Abstract: Electrochemical analyses of anisole, phenoxymethylboronic acid pinacol ester, tetra‐n‐butylammonium phenoxymethyltrifluoroborate, and their benzyloxy analogues were comparatively studied by using cyclic voltammetry measurements, and a marked β‐effect for organotrifluoroborates was found, which was indicated by experimental and theoretical aspects. Organotrifluoroborates were found to have much lower oxidation potentials than the corresponding boronic acid pinacol esters. The oxidation potentials of boronic aci… Show more

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Cited by 23 publications
(14 citation statements)
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“…The use of a redox catalyst to generate the alkyl radicals in the bulk solution can overcome some of the above‐mentioned problems (Scheme a) . However, overoxidation to carbocations is still difficult to avoid because the commonly employed radical precursors have higher oxidation potentials than many alkyl radicals, especially tertiary alkyl radicals and those with α‐stablization groups such as π‐systems and heteroatoms …”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…The use of a redox catalyst to generate the alkyl radicals in the bulk solution can overcome some of the above‐mentioned problems (Scheme a) . However, overoxidation to carbocations is still difficult to avoid because the commonly employed radical precursors have higher oxidation potentials than many alkyl radicals, especially tertiary alkyl radicals and those with α‐stablization groups such as π‐systems and heteroatoms …”
Section: Methodsmentioning
confidence: 99%
“…A variety of acyclic ( 22 ) and cyclic ( 23 – 29 ) secondary organotrifluoroborates participated in the photoelectrochemical C−H alkylation reaction, including those bearing a ketone carbonyl ( 27 ), a Boc‐protected amine ( 28 ), and a cyclic ether ( 29 ). α‐Alkoxyl and tertiary alkyl radicals are oxidized at potentials much lower than the organotrifluoroborates and thus are prone to undergo overoxidation to carbocations . Pleasingly, α‐alkoxyl ( 30 – 33 ) and tertiary ( 34 – 39 ) organotrifluoroborates also reacted successfully under modified conditions using either increased loading of the catalyst 3 or 4CzIPN as the catalyst.…”
Section: Methodsmentioning
confidence: 99%
“…Indeed, TBC used in excess for the transesterification step outcompetes other radical traps by fast transfer of hydrogen atoms to the alkyl radicals. Non‐chain approaches such as the generation of radicals through electrochemical oxidation of the ate complexes derived from R‐Bpin have been described . For instance, Lennox, Nutting, and Stahl reported the generation of benzylic radicals from ArCH(R)‐Bpin⋅NaOH complexes and were able to trap them with TEMPO (Scheme B) .…”
Section: Introductionmentioning
confidence: 99%
“…[*] E. AndrØ-Joyaux, [+] A. Kuzovlev, [+] scribed. [25,26] Forinstance,Lennox, Nutting,and Stahl reported the generation of benzylic radicals from ArCH(R)-Bpin•NaOH complexes and were able to trap them with TEMPO (Scheme 1B). [25] Similarly,Rasappan and Aggarwal and co-workers developed aradical-mediated protodeboronation reaction of R-Bpin upon treatment with phenyllithium to generate the corresponding ate complexes followed by an oxidative cleavage with Mn III salts in the presence of TBC (Scheme 1C).…”
Section: Introductionmentioning
confidence: 99%
“…Modification is a usual method to improve product qualities. For example, common catechols are mainly modified by methylation (sulfonation) [ 13 ], halogenation [ 14 , 15 ], Pechmann reaction [ 16 , 17 , 18 ], and boric esterification [ 19 ] which is moderately stable in air [ 20 ] due to its high affinity for diols [ 21 ], and is frequently used for recognizing carbohydrate [ 22 , 23 , 24 ]. Besides, some highly fluorinated catechol compounds have excellent cytotoxic activity against prostate cancer cells, and decrease their viability [ 25 ], giving rise to a gene delivery ability [ 26 ].…”
Section: Introductionmentioning
confidence: 99%