Enantioselective organocatalysis using SOMO activation

Abstract

Enantioselective organo-SOMO activation enables radical based functionalization of carbonyl compounds.

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

“…The amine catalyst is finely tuned so that only the si face of this radical cation is exposed for potential reaction with a SOMO nucleophile, e.g., allylsilane 37 , thus providing a high level of enantiocontrol. In addition to enantioselective allylation, a panel of other transformations 38 such as vinylation 39 , arylation 40 , alkynylation 41 , and alkylation 42 , 43 reactions have been also established. Besides, the SOMO activation strategy has been extended to the γ-alkylation of enal via a dienamine intermediate formed by condensation with proline-derived catalyst 5 .…”

Electrochemical oxidative C–H/S–H cross-coupling between enamines and thiophenols with H2 evolution

“…This strategy might provide a solution for the synthesis of vinyl sulfides by the cross-coupling of an alkene radical and a thiyl radical. It has been reported that an enamine can generate the enamine radical cation under oxidation and/or transition-metal catalyst conditions 6. And thiophenol can produce the thiyl radical which might couple with the enamine radical cation to furnish the vinyl sulfide.…”

Recent development and applications of semipinacol rearrangement reactions

“…9 (ref. [62][63][64] would form a radical cation that could add to the alkene of allylic alcohol 64, thus promoting the ring-enlargement rearrangement. A broad range of enantioenriched a-quaternary cyclopentanones can be accessed using this method.…”