Photochemical synthesis of N-adamantylhomoallylamines through addition of cyclic olefins to imines catalyzed by alumina grafted cadmium sulfide

Grafting cadmium sulfide onto alumina induces a small bandgap widening and a more significant lifetime variation of the light generated charge carriers from 0.76 microseconds measured for pristine CdS to 0.75, 0.86, and 1.20 microseconds found for CdS/Al2O3 containing 30, 20, and 9% of CdS, respectively. The quasi-Fermi level of electrons of -0.42 V (NHE) is not significantly changed. These alumina grafted semiconductor photocatalysts enable the linear addition of cyclopentene, cyclohexene, and alpha-pinene to N-adamantylimines affording novel homoallyladamantylamines in isolated yields of 21-85% through a regioselective C-C heterocoupling of intermediate allyl and alpha-aminobenzyl radicals. As by-products hydrodimers of the imine are formed by C-C homocoupling of the benzylic radicals. Different from heterocoupling, the homocoupling is a stereospecific process directed by the nature of the olefin employed in the reaction.

将硫化镉接枝到氧化铝上会导致一个小的带隙变宽，并且光生载流子的寿命发生更显著的变化，从原始硫化镉所测的0.76微秒分别变为含30%、20%和9%硫化镉的硫化镉/氧化铝的0.75、0.86和1.20微秒。 -0.42 V（相对于标准氢电极）的电子准费米能级没有显著变化。这些氧化铝接枝的半导体光催化剂能够使环戊烯、环己烯和α -蒎烯与N -金刚烷基亚胺进行线性加成，通过中间体烯丙基和α -氨基苄基自由基的区域选择性碳 - 碳异偶联，以21 - 85%的分离产率得到新型高烯丙基金刚烷基胺。作为副产物，亚胺的氢化二聚体通过苄基自由基的碳 - 碳同偶联形成。与异偶联不同，同偶联是一个由反应中所使用的烯烃性质决定的立体专一性过程。