Department of Applied Chemistry, Osaka University , 2-1 Yamada-oka, Suita 565-0871, Japan.
J Am Chem Soc. 2015 Dec 2;137(47):15007-14. doi: 10.1021/jacs.5b09775. Epub 2015 Nov 20.
Near-perfect stereoselectivity was attained in the diastereodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylates tethered to a glucose scaffold not by thermodynamically tuning the conformer equilibrium in the ground state but by kinetically controlling the conformer dynamics and reactivity in the excited state, which enabled us, after removal of the scaffold, to obtain a single enantiomer of chiral anti-head-to-head-cyclodimer in >99% optical and 96% chemical yield from an ensemble of four precursor conformers.
在通过葡萄糖支架连接的 2-蒽羧酸酯的非对映选择性[4+4]光环二聚反应中，通过动力学控制激发态构象动力学和反应性，而不是通过在基态下热力学调节构象平衡，实现了近乎完美的对映选择性。这使我们能够在除去支架后，从四个前体构象的混合物中以>99%的光学和 96%的化学收率获得手性反-头对头环二聚体的单一对映异构体。
