2020
DOI: 10.1002/ajoc.202000196
|View full text |Cite
|
Sign up to set email alerts
|

Selectfluor® Radical Dication (TEDA2+.) – A Versatile Species in Modern Synthetic Organic Chemistry

Abstract: In radical processes involving Selectfluor®, TEDA 2 + * (N-(chloromethyl)triethylenediamine) is often generated after an electron or fluorine transfer step. This is a highly reactive species that displays different and unique reactivity when compared to Selectfluor®: It can act as a hydrogen atom transfer (HAT), halogen atom transfer (XAT), or aminating reagent, as well as a powerful single electron oxidant. Despite this versatility, the use of TEDA 2 + * in synthetic processes remains highly underexplored. Th… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1

Citation Types

0
49
0

Year Published

2020
2020
2024
2024

Publication Types

Select...
7
1

Relationship

0
8

Authors

Journals

citations
Cited by 51 publications
(49 citation statements)
references
References 65 publications
0
49
0
Order By: Relevance
“…It should be noted here that Selectuor can be activated by photoirradiation, where the generated cation radical A is responsible for the hydrogen atom abstraction (HAA) during the C-H activation of various hydrocarbons. 25,26 Interestingly, acyl uoride 2a was also obtained when the reaction was triggered via photoirradiation (Scheme 3b). However, when compared to the photoirradiation approach, the CuBr 2 /Selectuor system showed higher efficiency, which suggests that the role of the copper species may not be that of an initiator, but that of a catalyst involved in the amide-cleavage process.…”
Section: Resultsmentioning
confidence: 99%
“…It should be noted here that Selectuor can be activated by photoirradiation, where the generated cation radical A is responsible for the hydrogen atom abstraction (HAA) during the C-H activation of various hydrocarbons. 25,26 Interestingly, acyl uoride 2a was also obtained when the reaction was triggered via photoirradiation (Scheme 3b). However, when compared to the photoirradiation approach, the CuBr 2 /Selectuor system showed higher efficiency, which suggests that the role of the copper species may not be that of an initiator, but that of a catalyst involved in the amide-cleavage process.…”
Section: Resultsmentioning
confidence: 99%
“…[28][29][30] These include fluorinating agents with nucleophilic, electrophilic and/or radical character, such as DAST, Selectfluor® (F-TEDA) and NFSI, which are able to mediate several types of fluorination reactions. [31][32][33][34][35][36] The discovery of such reagents represents a milestone in fluorination chemistry, and has subsequently led to the design of a great deal of new fluorination procedures. As such, a large portion of the modern catalytic methods to synthesise C(sp 3 )-F bonds typically utilise these "easy-to-handle" fluorinating agents.…”
Section: General Methods Of Fluorinationmentioning
confidence: 99%
“…nucleophilic, electrophilic, and radical fluorination. [31][32][33][34][35][36] In contrast to nucleophilic reactions, which are generally accepted to involve fluoride ions (F − ), electrophilic reactions are not thought to occur via the formation of formal fluoronium cations (F + ), which are unlikely to be formed due to their instability and the energy required to their formation. 17 For electrophilic fluorination, fluorine transfer is proposed to occur via two possible mechanisms; (i) single electron transfer (SET), or (ii) S N 2 nucleophilic substitution, in which a nucleophilic substrate attacks the fluorine atom, yielding the R-F bond.…”
Section: General Methods Of Fluorinationmentioning
confidence: 99%
“…[7] Among them, tertiary amine-derived cationic aminium radicals have recently been gaining attention as efficient HAT mediators. [8][9] The highly electrophilic nature of these radicals enables the selective abstraction of a hydrogen atom from hydridic C−H bonds. While aminium radicals derived from quinuclidine and its derivatives have been used for efficient HAT from substrates bearing C−H bonds adjacent to a heteroatom, [8] the more electrophilic dicationic aminium radical derived from Selectfluor ® can even abstract hydrogen atoms from the unactivated C−H bonds of hydrocarbons (Figure 1A).…”
mentioning
confidence: 99%
“…While aminium radicals derived from quinuclidine and its derivatives have been used for efficient HAT from substrates bearing C−H bonds adjacent to a heteroatom, [8] the more electrophilic dicationic aminium radical derived from Selectfluor ® can even abstract hydrogen atoms from the unactivated C−H bonds of hydrocarbons (Figure 1A). [9] Moreover, these methods sometimes show unique site-selectivity among C−H bonds with similar BDEs. [10] Despite these attractive features, the use of dicationic aminium radicals as HAT mediators has been limited to fluorination and a few other oxidative transformations, as this radical is mainly generated in situ from a (supra)stoichiometric amount of Selectfluor ® , which is known as a fluorine-atom transfer reagent and/or a strong oxidant.…”
mentioning
confidence: 99%