Carbonylative Cyclization of 2-Iodofluorobenzenes and 2-Aminophenols with Recyclable Palladium-Complexed Dendrimers on SBA-15: One-Pot Synthesis of Dibenzoxazepinones

IF 3.3 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry Pub Date : 2024-09-27 DOI:10.1021/acs.joc.4c01640

Qian Ye, Gang Xie, Wenyan Hao, Mingzhong Cai

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Abstract

A novel, efficient, and practical route to dibenzoxazepinones has been developed through a one-pot heterogeneous palladium-catalyzed aminocarbonylation/aromatic nucleophilic substitution (S_NAr) sequence starting from readily available 2-iodofluorobenzenes and 2-aminophenols. The carbonylative cyclization reaction proceeds smoothly in dimethyl sulfoxide (DMSO) at 120 °C with 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) as the base by using a polyamidoamine (PAMAM)-dendronized SBA-15-supported bidentate phosphine–palladium complex [G(1)-2P-Pd(OAc)₂-SBA-15] as the catalyst under 10 bar of CO, yielding a wide variety of dibenzo[b,e][1,4]oxazepin-11(5H)-one derivatives in good to excellent yields. Moreover, this new heterogenized dendritic palladium catalyst has competitive advantages in that it can be facilely recovered by simple filtration in air and recycled more than eight times without any significant loss of activity. The broad substrate scope, high functional group tolerance, and excellent palladium catalyst recyclability of the reaction make this approach a general, efficient, and economical method for the construction of valuable dibenzoxazepinone derivatives.

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2-Iodofluorobenzenes and 2-Aminophenols with Carbonylative Cyclization with Recyclable Palladium-Complexed Dendrimers on SBA-15：二苯并氧氮杂卓酮的一锅合成

从容易获得的 2-iodofluorobenzenes 和 2-aminophenols 开始，通过单锅异质钯催化的氨基羰基化/芳香族亲核取代 (SNAr) 顺序，开发出了一条新颖、高效和实用的二苯并氧氮杂卓酮路线。羰基化环化反应在二甲基亚砜（DMSO）中于 120 °C下顺利进行，1,8-二氮杂双环（5.4.0）十一-7-烯（DBU）为碱，在 10 bar CO 的条件下，使用聚氨基胺（PAMAM）-二膦化 SBA-15-supported bidentate phosphine-palladium complex [G(1)-2P-Pd(OAc)2-SBA-15]作为催化剂，以良好至优异的收率生成了多种二苯并[b,e][1,4]氧氮杂卓-11(5H)-酮衍生物。此外，这种新型异质化树枝状钯催化剂具有竞争优势，只需在空气中进行简单过滤即可轻松回收，并可循环使用八次以上而不会明显丧失活性。该反应具有广泛的底物范围、高官能团耐受性和出色的钯催化剂可回收性，使这种方法成为一种通用、高效和经济的方法，可用于构建有价值的二苯并氧氮杂卓酮衍生物。

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来源期刊

The Journal of Organic Chemistry 化学-有机化学

CiteScore

6.20

自引率

11.10%

发文量

1467

审稿时长

2 months

期刊介绍： The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.