Fluoroalkylation of Diazo Compounds with Diverse R_fn Reagents

Abstract

Progress in the transition-metal-catalyzed or -free fluoroalkylation of diazo compounds with different types of fluoroalkyl (R fn ) transfer reagents is summarized in this review. Special attention is focused on the straightforward trifluoromethylation, gem-difluoroolefination, trifluoromethoxylation, fluoroalkylthiolation, and trifluoromethylselenolation of diazo substrates. The mechanistic insights and the application of some of the products are also discussed in this article. We believe that this review will inspire both young and experienced chemists to further study the direct fluoroalkylation of diazo compounds as an efficient and convenient way to build complex fluorinecontaining molecules.[a] S.

Synthesis and Biological Evaluation of CF3Se‐Substituted α‐Amino Acid Derivatives

“…Selenium is an essential element for organisms and its deficiency induces a lot of pathologies in both humans and animals [10] . The CF 3 Se functionality, possessing unique electrosteric and lipophilic characteristics, has been confirmed as an interesting alternative to regulate the properties of target molecules [9e–g] . As a part of our continuing interest in the progress of trifluoromethylselenolation methodologies with [Me 4 N][SeCF 3 ] and discovery of CF 3 Se‐containing bioactive molecules, [11] we investigated in this work the synthesis and biological activity of several CF 3 Se‐substituted α‐amino acid derivatives from the readily available [Me 4 N][SeCF 3 ] reagent.…”

Advances in the Development of Trifluoromethoxylation Reagents

“…Both, moderately electron-donating or electron-withdrawing substituents on the phenyl ring had no significant influence on the yields of trifluoromethoxylated products. However, the strong electron- A silver-mediated direct trifluoromethoxylation of α-diazo esters was also performed using TFMT as trifluoromethoxide anion source for α-trifluoromethoxylation of esters under mild reaction conditions [113,114]. The reaction of alkyl α-diazo arylacetates 40 (Scheme 27) was typically carried out with TFMT 36 and AgF in MeCN at −30 to 10 • C providing α-trifluoromethoxyl arylacetates 42 in up to 90% yield.…”

Markovnikov-Type Hydrotrifluoromethylchalcogenation of Unactivated Terminal Alkenes with [Me4N][XCF3] (X = S, Se) and TfOH

“…Recently, the special stereoelectronic and physicochemical properties originating from the association of the trifluoromethyl (CF 3 ) moiety with chalcogens (e.g., oxygen, sulfur and selenium) have been well documented [ 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. The OCF 3 and SCF 3 groups possess strong electronegativity, considerable steric hindrance, and high lipophilicity, which can significantly change the bioactivity of a molecule [ 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ]. The least-studied SeCF 3 group represents another important functionality, exhibiting a valuable stereoelectronic nature and lipophilicity, and has immense potential to modulate the potency of agrochemicals and pharmaceuticals [ 11 , 12 , 13 ].…”

“…Although selenium substances have shown very useful biological activities and have been widely utilized in drug design and development [ 14 , 15 , 16 , 17 , 18 ], to our knowledge, the uses of SeCF3-containing compounds have rarely been explored in comparison with those non-fluorinated analogues. This may be attributed to the lack of structural diversity, sufficient synthetic methods, and imperative biological investigation of the trifluoromethylselenolated compounds [ 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. Thus, continuously developing efficient approaches for the construction of different types of SeCF 3 -containing organic scaffolds for future function studies is highly sought-after.…”

“…Over the past few decades, fluorinated compounds have attracted great attention in various fields ranging from materials to life sciences because of their unique properties imparted by fluorine [1]. Recently, the special stereoelectronic and physicochemical properties originating from the association of the trifluoromethyl (CF 3 ) moiety with chalcogens (e.g., oxygen, sulfur and selenium) have been well documented [2][3][4][5][6][7][8][9][10][11][12][13]. The OCF 3 and SCF 3 groups possess strong electronegativity, considerable steric hindrance, and high lipophilicity, which can significantly change the bioactivity of a molecule [2][3][4][5][6][7][8][9][10].…”