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Synlett 2023; 34(18): 2187-2192
DOI: 10.1055/a-2110-5359
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Modern Boron Chemistry: 60 Years of the Matteson Reaction

Remote Back Strain: A Strategy for Modulating the Reactivity of Triarylboranes

Mahiro Sakuraba
a   Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Taichi Morishita
a   Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Taiki Hashimoto
a   Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Sensuke Ogoshi∗
a   Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Yoichi Hoshimoto  ∗
a   Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
b   Center for Future Innovation (CFi), Division of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
› Author AffiliationsThis project was supported by the Environment Research and Technology Development Fund (JPMEERF20211R01 to Y.H.) of the Environmental Restoration and Conservation Agency of the Ministry of the Environment of Japan, and Grants-in-Aid for Transformative Research Area (A) Digitalization-driven Transformative Organic Synthesis (JSPS KAKENHI Grant 22H05363 to Y.H.). Y.H. acknowledges financial supports from the Yazaki Memorial Foundation for Science and Technology, the Kansai Research Foundation for Technology Promotion, and the Takeharakenzai Alpsclean Co., Ltd. M.S. gratefully acknowledges a JST SPRING grant (JPMJSP2138).
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Abstract

A strategy for modulating the Lewis acidity of triarylboranes is proposed based on the concept of remote back strain. Steric repulsion and noncovalent interactions, both generated between the aryl meta-substituents of triarylboranes, are found to be critical for determining the strength of the remote back strain. Applying this concept, we synthesized B[2,6-F2-3,5-(TMS)2-C6H]3 and the liquid B[2,6-F2-3,5-(allyl)2-C6H]3 and we demonstrated their superior catalytic activity for the hydrogenation of quinoline relative to B(C6F5)3 or B(2,6-F2C6H3)3. Moreover, we established the first example of the catalytic hydrogenation of quinoline by using B[2,6-F2-3,5-(allyl)2-C6H]3 in the presence of a gaseous 1:1:1 molar mixture of H2, CO, and CO2.

Key words

triarylboranes - Lewis acids - frustrated Lewis pairs - hydrogenation - boron catalysis - hydrogen separation

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2110-5359.
  • Supporting Information


Publication History

Received: 30 May 2023

Accepted after revision: 14 June 2023

Accepted Manuscript online:
14 June 2023

Article published online:
14 September 2023

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