Luo Youran, Gutiérrez-Bonet Álvaro, Matsui Jennifer K, Rotella Madeline E, Dykstra Ryan, Gutierrez Osvaldo, Molander Gary A
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323 (USA).
Wuyuzhang Honors College, 29, Wangjiang Road, Chengdu, Sichuan, 610064 (China).
ACS Catal. 2019 Sep 6;9(9):8835-8842. doi: 10.1021/acscatal.9b02458. Epub 2019 Aug 28.
Herein, the introduction of oxa- and azabenzonorbornadienes into photoredox/nickel dual catalysis in a regioselective and diastereoselective transformation is disclosed. The inherent advantages of this dual catalytic system allow the use of alkyl motifs forming exclusively -1,2-dihydro-1-naphthyl alcohol backbones using readily accessible 4-alkyl-1,4-dihydropyridines (DHPs). Whereas previous studies have emphasized the use of nucleophilic organometallic coupling partners, this protocol grants access to a rather unexplored core featuring alkyl residues, while avoiding the use of highly reactive organometallic species (i.e., M = Al, Mg, Li, Zn, Zr). DFT calculations support a oxidative addition/reductive elimination mechanism, followed by a Curtin-Hammett scenario that controls the regioselectivity of the process, unlike previously reported transformations that proceed via a carbometalation/ -oxygen elimination mechanism.
本文公开了将氧杂和氮杂苯并降冰片二烯引入光氧化还原/镍双催化体系中，实现区域选择性和非对映选择性转化。这种双催化体系的固有优势在于，利用易于获得的4-烷基-1,4-二氢吡啶（DHP），仅形成-1,2-二氢-1-萘醇骨架的烷基基团。尽管先前的研究强调使用亲核有机金属偶联伙伴，但该方案提供了一个相对未被探索的含有烷基残基的核心结构，同时避免使用高活性有机金属物种（即M = Al、Mg、Li、Zn、Zr）。密度泛函理论（DFT）计算支持氧化加成/还原消除机制，随后是控制该过程区域选择性的柯廷-哈米特（Curtin-Hammett）情况，这与先前报道的通过碳金属化/氧消除机制进行的转化不同。
