Rhodium-Catalyzed Coordination-Assisted Regioselective and Migratory Three-Point Double Annulation of o-Alkenyl Phenols with Tertiary Propargyl Alcohols,Organic Letters

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Rhodium-Catalyzed Coordination-Assisted Regioselective and Migratory Three-Point Double Annulation of o-Alkenyl Phenols with Tertiary Propargyl Alcohols
Organic Letters ( IF 4.9 ) Pub Date : 2022-07-11 , DOI: 10.1021/acs.orglett.2c01819
Attunuri Nagireddy _{1,

2} , Ramesh Kotipalli _{1,

2} , Jagadeesh Babu Nanubolu _{1,

3} , Maddi Sridhar Reddy _{1,

2}

Affiliation

We disclose herein a Rh(III)-catalyzed migratory three-point double annulation of o-alkenyl phenols with propargyl alcohols for de novo construction of naphtho furan derivatives in a regio- and chemoselective manner. The protocol orchestrates two new rings with four new bonds in one operation without the need for any additive. Necessary labeled and control experiments are conducted to elucidate the reaction mechanism. A tertiary hydroxyl group is found to be crucial both for controlling the regioselective insertion of alkyne through chelation with rhodium to form a key spiro cyclic intermediate and for forcing ring expansion via unusual and selective olefin reshuffling, apart from forming an extra (furan) ring. The protocol is scalable and shows tolerance for late stage functionalization of natural products.

中文翻译：

铑催化配位辅助的区域选择性和迁移三点双环化邻烯基酚与叔炔丙醇

我们在此公开了 Rh(III) 催化的邻烯基酚与炔丙醇的迁移三点双环化，用于以区域选择性和化学选择性的方式从头构建萘并呋喃衍生物。该协议在一次操作中编排了两个新环和四个新键，而无需任何添加剂。进行必要的标记和对照实验以阐明反应机理。除了形成额外的（呋喃）环外，叔羟基被发现对于通过与铑螯合以形成关键的螺环中间体来控制炔烃的区域选择性插入以及通过不寻常和选择性的烯烃重排来强制扩环都是至关重要的。该协议具有可扩展性，并显示出对天然产物后期功能化的耐受性。

更新日期：2022-07-11

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