2. Academic Validation
  3. Tetraborylation of p-Benzynes Generated by the Masamune-Bergman Cyclization through Reaction Design Based on the Reaction Path Network

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

  • JACS Au. 2024 Jun 20;4(7):2578-2584. doi: 10.1021/jacsau.4c00302.
Soichiro Nakatsuka 1 2,  Seiji Akiyama 1 3,  Yu Harabuchi 1 3,  Satoshi Maeda 1 2 3 4,  Yuuya Nagata 1 3
Affiliations

Affiliations

  • 1 ERATO Maeda Artificial Intelligence in Chemical Reaction Design and Discovery Project, JST, Sapporo 060-0810, Hokkaido, Japan.
  • 2 Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Hokkaido, Japan.
  • 3 Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Hokkaido, Japan.
  • 4 Research and Services Division of Materials Data and Integrated System (MaDIS), National Institute for Materials Science (NIMS), Tsukuba 305-0044, Ibaraki, Japan.
PMID: 39055142 DOI: 10.1021/jacsau.4c00302
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 p-benzynes generated from 1,2-diethynylbenzene derivatives, using bis(pinacolato)diborane(4) (B2pin2). 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 B2pin2 gave the tetraborylated products in good yields (up to 58%). It is quite intriguing that the two carbons of p-benzyne behave formally as dicarbenes in this reaction.

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