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基于反应路径网络的反应设计通过Masamune-Bergman环化生成的-苯炔的四硼化反应

Tetraborylation of -Benzynes Generated by the Masamune-Bergman Cyclization through Reaction Design Based on the Reaction Path Network.

作者信息

Nakatsuka Soichiro, Akiyama Seiji, Harabuchi Yu, Maeda Satoshi, Nagata Yuuya

机构信息

ERATO Maeda Artificial Intelligence in Chemical Reaction Design and Discovery Project, JST, Sapporo 060-0810, Hokkaido, Japan.

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Hokkaido, Japan.

出版信息

JACS Au. 2024 Jun 20;4(7):2578-2584. doi: 10.1021/jacsau.4c00302. eCollection 2024 Jul 22.

DOI:10.1021/jacsau.4c00302
PMID:39055142
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11267532/
Abstract

Designing the reactant molecule of an initial reaction, based on quantum chemical pathway exploration, enabled us to access a new reaction, i.e., the tetraborylation reaction of -benzynes generated from 1,2-diethynylbenzene derivatives, using bis(pinacolato)diborane(4) (Bpin). Based on the reaction path network generated via the artificial-force-induced reaction (AFIR) method, desired and undesired paths were identified and used to modify the chemical structure of the reactant. After the in silico screening, the optimal structure of the reactant was determined to be a 1,2-diethynylbenzene derivative with a butylene linker. The reaction of the optimized reactant and its derivatives with an excess of Bpin gave the tetraborylated products in good yields (up to 58%). It is quite intriguing that the two carbons of -benzyne behave formally as dicarbenes in this reaction.

摘要

基于量子化学路径探索设计初始反应的反应物分子，使我们能够实现一种新反应，即使用双(频哪醇合)二硼烷(4)（Bpin）使1,2 - 二乙炔基苯衍生物生成的对 - 苯炔发生四硼化反应。基于通过人工力诱导反应（AFIR）方法生成的反应路径网络，识别出期望和不期望的路径，并用于修饰反应物的化学结构。经过计算机筛选后，确定反应物的最佳结构为带有丁烯连接基的1,2 - 二乙炔基苯衍生物。优化后的反应物及其衍生物与过量的Bpin反应，以良好的产率（高达58%）得到四硼化产物。非常有趣的是，在该反应中对 - 苯炔的两个碳原子形式上表现为双卡宾。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/5b7b5b948f08/au4c00302_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/3e40fffff5fb/au4c00302_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/da35e4e73ccd/au4c00302_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/6a3faab977d8/au4c00302_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/d08c32b19716/au4c00302_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/5b7b5b948f08/au4c00302_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/3e40fffff5fb/au4c00302_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/da35e4e73ccd/au4c00302_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/6a3faab977d8/au4c00302_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/d08c32b19716/au4c00302_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/909c/11267532/5b7b5b948f08/au4c00302_0005.jpg

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