Achiral Counteranion-Induced Reversal of Enantioselectivity in Ni(II)-Catalyzed Friedel–Crafts Alkylation/Annulation of 2-Naphthols,Organic Letters

当前位置： X-MOL 学术 › Org. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Achiral Counteranion-Induced Reversal of Enantioselectivity in Ni(II)-Catalyzed Friedel–Crafts Alkylation/Annulation of 2-Naphthols
Organic Letters ( IF 4.9 ) Pub Date : 2024-07-23 , DOI: 10.1021/acs.orglett.4c02156
Chen-Ying Hou ₁ , Chun Yang ₁ , Yin Tian ₂ , Ming-Sheng Xie ₁ , Hai-Ming Guo ₁

Affiliation

An achiral counteranion-induced reversal of enantioselectivity in Ni(II)-catalyzed Friedel–Crafts alkylation/annulation of 2-naphthols with β,γ-unsaturated α-keto esters was achieved. Using imidazolidine pyrroloimidazolone pyridine as the ligand and Ni(acac)₂ as the Lewis acid, diverse naphthopyran derivatives were obtained in good yields (up to 94% yield) and high enantioselectivities (up to 99% ee). In the presence of Ni(OTf)₂ as the Lewis acid, a series of chiral naphthopyran derivatives were obtained in good yields and with a controlled switch in stereoselectivity. DFT calculations reveal that the achiral counteranions regulate H-bonding interactions between counteranions with the N–H of the ligand and the O–H of 2-naphthol.

中文翻译：

Ni(II) 催化的 2-萘酚傅克烷基化/成环反应中非手性抗衡阴离子诱导的对映选择性逆转

在 Ni(II) 催化的 2-萘酚与 β,γ-不饱和 α-酮酯的弗里德尔-克来福特烷基化/成环反应中，实现了非手性抗衡阴离子诱导的对映选择性逆转。以咪唑烷吡咯并咪唑啉酮吡啶为配体，Ni(acac) ₂为Lewis酸，以良好的产率（高达94％的产率）和高的对映选择性（高达99％ee）获得了多种萘并吡喃衍生物。在Ni(OTf) ₂作为路易斯酸存在下，以良好的产率获得了一系列手性萘并吡喃衍生物，并具有可控的立体选择性转换。 DFT 计算表明，非手性抗衡阴离子调节抗衡阴离子与配体的 N-H 和 2-萘酚的 O-H 之间的 H 键相互作用。

更新日期：2024-07-23

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南