Tsuji Yasutaka, Kon Kazumasa, Horibe Takahiro, Ishihara Kazuaki
Graduate School of Engineering, Nagoya University, B2-3(611), Furo-cho, Chikusa, Nagoya, 464-8603, Japan.
Venture Business Laboratory, Nagoya University, B2-4, Furo-cho, Chikusa, Nagoya, 464-814, Japan.
Chem Asian J. 2023 Apr 3;18(7):e202300019. doi: 10.1002/asia.202300019. Epub 2023 Feb 13.
A chiral amidophosphate-N-iodosuccinimide cooperative catalysis has been developed for the site-, diastereo-, and enantioselective iodocyclization of 2-geranylarenols with molecular iodine to give the corresponding iodo-containing polycyclic compounds with good levels of selectivity. This is the first example of a catalytic enantioselective iodocarbocyclization. A reactive chiral iodonium species is generated from molecular iodine via the dual halogen-bonding interactions with a chiral Lewis base and Lewis acid. The sterically demanding 3,3'-substituents of the chiral BINOL-derived amidophosphate are critical to induce the site-selective iodination at the less-hindered terminal alkenyl moiety of 2-geranylarenols.
已开发出一种手性氨基磷酸酯- N -碘代琥珀酰亚胺协同催化体系，用于2-香叶基芳醇与分子碘的位点、非对映和对映选择性碘环化反应，以高选择性得到相应的含碘多环化合物。这是催化对映选择性碘碳环化反应的首例。通过与手性路易斯碱和路易斯酸的双重卤素键相互作用，由分子碘生成了一种活性手性碘鎓物种。手性联萘酚衍生的氨基磷酸酯的空间位阻较大的3,3'-取代基对于在2-香叶基芳醇的位阻较小的末端烯基部分诱导位点选择性碘化至关重要。
