Quantification of the Electrophilicity of Benzyne and Related Intermediates

Abstract

The determination of reactivity parameters for short-lived intermediates provides an indispensable tool for synthetic design. Despite that electrophilicity parameters have now been established for more than 250 reactive species, the corresponding parameters for benzyne and related intermediates have not been uncovered. We report a study that has allowed for the quantification of benzyne’s electrophilicity parameter. Our approach relies on the strategic use of the diffusion-clock method and also provides electrophilicity parameters E for other substituted arynes.

Cyclic Alkyne Approach to Heteroatom‐Containing Polycyclic Aromatic Hydrocarbon Scaffolds

“…However, in recent years, strained cyclic alkynes have resurfaced and have been widely employed in synthetic methodology studies . Additionally, such efforts have led to a greater understanding of aryne and cyclic alkyne reactivity and regioselectivities, and a host of synthetic applications impacting catalysis, agrochemistry, pharmaceuticals, and academia . A selection of important arynes and cyclic alkynes are shown in Figure …”

Leveraging Fleeting Strained Intermediates to Access Complex Scaffolds

“…Moreover, it should be noted that arynes can be generated under exceedingly mild, safe, and operationally simple fluoride-based reaction conditions, thanks to the advent of Kobayashi silyl triflates. 19 − 22 In turn, chemists have sought to leverage the synthetic utility of these once controversial species, in addition to deepening our fundamental understanding through electrophilicity studies 23 and regioselectivity studies. 24 − 26 …”

Cyclic Alkyne Approach to Heteroatom-Containing Polycyclic Aromatic Hydrocarbon Scaffolds

“…1,2,3,4,5,6,7,8,9,10 Additionally, such efforts have led to a greater understanding of aryne and cyclic alkyne reactivity and regioselectivities, which in turn, has enabled predictions. 11,12,13,14,15,16 The rapid expansion of the field of cyclic alkyne chemistry has led to a host of synthetic applications. For example, arynes and cyclic alkynes have been used as building blocks in the synthesis of catalyst ligands, 17 agrochemicals, 18 pharmaceuticals, and countless natural products.…”

“…[1][2][3][4] Additionally,such efforts have led to ag reater understanding of aryne and cyclic alkyne reactivity and regioselectivities, [5][6][7] and ah ost of synthetic applications impacting catalysis, [8] agrochemistry, [9] pharmaceuticals,a nd academia. [1][2][3][4] Additionally,such efforts have led to ag reater understanding of aryne and cyclic alkyne reactivity and regioselectivities, [5][6][7] and ah ost of synthetic applications impacting catalysis, [8] agrochemistry, [9] pharmaceuticals,a nd academia.…”