3-Acetoxyquinuclidine as Catalyst in Electron Donor–Acceptor Complex-Mediated Reactions Triggered by Visible Light

Abstract

Only substoichometric amounts (10 to 25 mol%) were needed to trigger the desired reaction. The outcome could be tuned by selecting the nature of the formed radical to perform amino-and hydro-decarboxylation, dimerization, and cyclization reactions. Importantly, no external additives were needed in this reaction.

Radical Perfluoroalkylation Enabled by a Catalytically Generated Halogen Bonding Complex and Visible Light Irradiation

“…Five-membered nitrogen-, sulfur-and oxygenbased heteroarenes (1-5) were all well tolerated. Electron-rich arenes also reacted well under our reaction conditions (6)(7)(8)(9). Moreover, the reaction with 1,3,5-trimethoxybenzene (6) could be performed at 1 mmol scale without any loss in reactivity.…”

Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

“…In 2019, Bosque and Bach [ 41 ] reported that 3-acetoxyquinuclidine (q-OAc) could be utilized as an electron-donor catalyst to form an EDA complex with electron acceptor 158 , and then a molecule of carbon dioxide was removed under 455 nm light irradiation, giving decarboxylation product 159 ( Scheme 55 ). It was found that many ester groups can be activated by the structural motif of tetrachlorophthalimide in 158 .…”

The Morita–Baylis–Hillman reaction for non-electron-deficient olefins enabled by photoredox catalysis

“…[20][21][22][23][24][25][26][27][28] In a few cases, a quinuclidinium radical cation also works as an oxidant that reacts with nucleophilic radicals or transient-metal intermediate through single electron transfer Please do not adjust margins Please do not adjust margins (SET). 29,30 However, as an electrophilic species, the quinuclidinium radical cation adds to olefin has not yet been revealed. We suspect that the obtained β-quinuclidinium radical species, structurally similar to β-quinuclidinium carbanion zwitterions, may provide an opportunity to achieve the MBH reaction for non-electron-deficient olefins (Scheme 1C).…”