Heat- or light-induced acylarylation of unactivated alkenes towards 3-(α-acyl) indolines

Abstract

<p>A heat- or photoredox/iron dual catalysis-enabled dehydrogenative acylarylation of N-allyl anilines leading to 2-substituted 3-(α-acyl) indolines with a quaternary stereogenic center is presented, with unactivated alkenic bonds as radical acceptors...</p>

Visible-Light-Induced Formation of Thiavinyl 1,3-Dipoles: A Metal-Free [3+2] Oxidative Cyclization with Alkynes as Easy Access to Thiophenes

“…First, the reactions of 1a and 2a were investigated with the light off/on over a period of time under the optimal reaction conditions. The reaction proceeded well under visible light irradiation, but no further transformation was observed without light irradiation (Figure a), indicating the continuous irradiation of visible light is essential for this catalytic reaction. , Furthermore, the UV–vis absorption spectra (Figure b) confirmed that Acr + -Mes-Ph BF 4 – (Ps-B) is the best photosensitizer as the sole catalyst tested in this [3+2] oxidative cyclization. The Stern–Volmer emission quenching studies (Figure c) determined that polarized ketene dithioacetals 1 more easily quench the excited photosensitizer than alkynes do.…”

Copper-promoted difunctionalization of unactivated alkenes with silanes

“…On the basis of previous reports 9 b,i , m ,16–25 and above experimental results, a possible mechanism was proposed and is depicted in Scheme 3. In the beginning, the thermal decomposition of DTBP leads to the formation of the t -butoxyl radical which can generate methyl radicals by a β-cleavage pathway.…”

“…For example, acetonitrile (CH 3 CN), azodiisobutyrodinitrile (AIBN), cyclohexane, benzaldehyde, tetrahydrofuran (THF), toluene, acetone, perfluorobutyl iodide ( n -C 4 F 9 I), dimethyl phosphite (HPO(OMe) 2 ) and trifluoromethylating agents have been used as the radical precursor to construct indoline structures in recent years. 16–25 Although remarkable efforts have been made in this field, the silylarylation of unactivated alkenes for the synthesis of 3-silyl indolines has not been studied. As part of our continuous studies on C–H functionalization 26 and organosilicon chemistry, 27 herein, we report the silylation of unactivated alkenes with silanes through a free-radical cascade process to construct 3-silyl indoline compounds (Scheme 1d).…”

Organic thermally activated delayed fluorescence (TADF) compounds used in photocatalysis

“…Two examples exist depicting the use of 4CzIPN in combination with an iron co-catalyst: the acylarylation of unactivated alkenes towards the synthesis of 3-(a-acyl) indolines (Fig. 112a); 280 and the reduction of CO 2 (Fig. 112b).…”