Trifluoromethylthiolative spirocyclization of biaryl ynones without leaving groups on the para-position of dearomatized aryl rings

Abstract

A direct and efficient strategy for the oxiditive spirocyclization of biaryl ynones has been developed, where nonsubstituted groups were on the para-position of dearomative aryl rings. This cascade reaction uses...

Progress in the Construction of Spirocyclohexadienones via Alkyne-Involving Dearomatization

“…图式 16 磺酰基螺[5,5]三烯酮的合成 Scheme 16 Synthesis of sulfonated spiro [5,5]trienones 过硫酸钾(K 2 S 2 O 8 )作用下产生三氟甲硫基自由基, 进而 与联芳基炔酮底物进行反应, 通过 6-exo-trig 环化实现 炔烃的三氟甲硫基化碳环化, 得到了一系列含 SCF 3 基 的螺 [5,5]三烯酮衍生物(Scheme 17a). 霍中洋等 [43] 也通 过类似的策略, 在 t BuOOH 存在下实现了远端苯环无离 去 基 团 的 联 芳 基 炔 酮 底 物 的 去 芳 构 化 反 应 (Scheme 17b). 2021 年, 杨文超课题组 [44] 报道了一种通过电化学 方法产生三氟甲硫基化自由基的方法, 避免了过量过硫 酸盐的使用, 条件更加温和(Scheme 17c).…”

Visible‐light Catalysed Trifluoromethylthiolation and Related Dearomative Spirocyclizations

“…[10] In 2022, Yang and Huo groups realized the synthesis of SCF 3 -containing spiro [5.5]trienone featuring K 2 S 2 O 8 promoted radical cyclization at elevated temperature. [11][12] Ackermann developed a tricyclic 6-7-6 fused system via electrooxidative radical cyclization using ArSO 2 Na. [13] Wang reported an electrochemical radical cyclization of biaryl ynones using AgSCF 3 .…”

“…For example, Liu reported Mn(III) mediated radical dearomatization of biaryl ynones with sodium sulfinates [10] . In 2022, Yang and Huo groups realized the synthesis of SCF 3 ‐containing spiro[5.5]trienone featuring K 2 S 2 O 8 promoted radical cyclization at elevated temperature [11–12] …”

AgSCF3 Radical Addition Based on an Oxidant-Free α,β-Amide (Trifluoromethyl)sulfanylation Reaction

“…2c,3e,4,5 Recently, efficient radical-type protocols for constructing the C-SCF 3 moiety by using a combination of AgSCF 3 and an oxidant have drawn great attention, but only a few protocols have focused on the difunctionalization of alkenes. [6][7][8] Scheme 1 Bioactive molecules containing SCF 3 , and common strategies for the (trifluoromethyl)sulfanylation of olefins Compared with (trifluoromethyl)sulfanylation reactions involving aromatic hydrocarbons 4a,f,9-13 or alkynes, [15][16][17][18][19][20][21][22][23][24][25] there are few reports on the (trifluoromethyl)sulfanylation reaction of olefins. 25 Many natural products and active drug molecules containing (trifluoromethyl)sulfanyl groups are obtained through the (trifluoromethyl)sulfanylation reaction of olefins.…”