Control of Conformer Population and Product- and Stereoselectivity in Competitive Photocyclization/Rearrangement of Chiral Donor-Acceptor Dyad
Control of Conformer Population and Product- and Stereoselectivity in Competitive Photocyclization/Rearrangement of Chiral Donor-Acceptor Dyad
复制标题
手性供体-受体二元体竞争性光环化/重排中适形体群体和产物选择性和立体选择性的控制
DOI：
10.1021/ja302768w
复制
发表时间：
2012
影响因子：
15
通讯作者：
Y. Inoue
中科院分区：
文献类型：
--
作者：
E. Nishiuchi;T. Mori;Y. Inoue
通过理论和实验检查评估的构象异构体数量和每个构象异构体的相对激发效率，使我们能够通过照射波长、溶剂极性和反应温度精确控制手性供体-受体（D/A）二联体的竞争性光环化/重排反应的化学和非对映选择性。操纵基态和激发态构象异构体平衡对于严格控制分子内 D/A 系统至关重要，这与相关分子间系统中涉及的相当不同的激发态物种形成鲜明对比。
The conformer population and the relative excitation efficiency of each conformer, assessed by theoretical and experimental examinations, enabled us to precisely control the chemo- and diastereoselectivities of the competitive photocyclization/rearrangement reaction of a chiral donor–acceptor (D/A) dyad by irradiation wavelength, solvent polarity, and reaction temperature. Manipulating the ground- and excited-state conformer equilibria is essential for critically controlling the intramolecular D/A system, in sharp contrast to the rather divergent excited species involved in relevant intermolecular systems.