The direct incorporation of alkanes and CO into value-added chiral products through alkane carbonylation is a desirable transformation; however, it remains inefficient. The carbonylation of alkanes via photoirradiated radical addition to CO requires mild reaction conditions but suffers from low conversion due to equilibrium constraints. Here an equilibrium-leveraging strategy that combines alkane carbonylation with various enantioselective transformations is reported. The combination of tetra-n-butylammonium decatungstate and chiral sodium phosphate catalysts enables alkane carbonylation/enantioselective Mannich reaction and alkane carbonylation/enantioselective radical addition cascade processes for the enantioselective synthesis of β-amino and α-amino ketones from alkanes, CO and anilines by breaking the equilibrium of reversible photocatalytic C–H carbonylation. While both reactions can tolerate a broad scope of cyclic alkanes and anilines, the synthetic method to synthesize β-amino ketones can use a range of aliphatic ketones as substrates. The synthetic process to form β-amino ketones can be readily scaled-up through use of an integrated continuous-flow and batch set-up, providing efficient gram-scale synthesis. Mechanistic studies reveal that the synthesis of α-amino ketones proceeds through the asymmetric addition of an acyl radical to an imine intermediate.

通过烷烃羰基化将烷烃和CO直接引入增值手性产物是一种理想的转化；然而，它仍然效率低下。通过光照射自由基加成至 CO 进行烷烃的羰基化需要温和的反应条件，但由于平衡限制，转化率较低。这里报道了一种将烷烃羰基化与各种对映选择性转化相结合的平衡杠杆策略。四正丁基十钨酸铵和手性磷酸钠催化剂的组合可实现烷烃羰基化/对映选择性曼尼希反应和烷烃羰基化/对映选择性自由基加成级联过程，用于从烷烃、CO和苯胺对映选择性合成β-氨基和α-氨基酮打破了可逆光催化C-H羰基化的平衡。虽然这两种反应都可以耐受广泛的环烷烃和苯胺，但合成 β-氨基酮的合成方法可以使用一系列脂肪族酮作为底物。通过使用集成的连续流和间歇装置，形成 β-氨基酮的合成过程可以很容易地扩大规模，从而提供有效的克级合成。机理研究表明，α-氨基酮的合成是通过酰基自由基不对称加成到亚胺中间体上进行的。