Modulation of Lewis Acidity and Steric Parameters in Cyclic Boronates: Copper-Catalyzed Internal-Selective Borylation of Challenging Terminal Alkynes

The installation of a boron functionality into a more substituted carbon of terminal alkynes in copper-catalyzed borylations with diborons is still a challenging subject, primarily due to the intrinsic Lewis acidity of boron moieties such as B­(pin), which typically favor addition to a terminal carb...

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Published inACS Catalysis Vol. 14; no. 17; pp. 12694 - 12703
Main Authors Tsushima, Takumi, Nakamoto, Masaaki, Yoshida, Hiroto
Format Journal Article
LanguageEnglish
Japanese
Published American Chemical Society 06.09.2024
American Chemical Society (ACS)
Subjects
copper catalysis
steric properties of cyclic boronate
terminal alkynes
boron-Lewis acidity
diborons
internal selectivity
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Abstract The installation of a boron functionality into a more substituted carbon of terminal alkynes in copper-catalyzed borylations with diborons is still a challenging subject, primarily due to the intrinsic Lewis acidity of boron moieties such as B­(pin), which typically favor addition to a terminal carbon. We disclose herein that the copper-catalyzed internal-selective hydroboration of a variety of challenging terminal alkynes, including sterically demanding and electron-rich aryl variants, is feasible using commercially available, six-membered bis­(hexylene glycolato)­diboron [B2(hex)2]. This observation underscores that subtle changes in boronate-Lewis acidities associated with ring size markedly influence the regioselectivities of the borylcupration step. Furthermore, this study reveals that the reduced steric bulk of boronate moieties, as well as diminished Lewis acidities, serve as pivotal factors contributing to internal selectivity. This provides crucial insights into the regiocontrol in the copper-catalyzed borylations of terminal alkynes.
AbstractList The installation of a boron functionality into a more substituted carbon of terminal alkynes in copper-catalyzed borylations with diborons is still a challenging subject, primarily due to the intrinsic Lewis acidity of boron moieties such as B­(pin), which typically favor addition to a terminal carbon. We disclose herein that the copper-catalyzed internal-selective hydroboration of a variety of challenging terminal alkynes, including sterically demanding and electron-rich aryl variants, is feasible using commercially available, six-membered bis­(hexylene glycolato)­diboron [B2(hex)2]. This observation underscores that subtle changes in boronate-Lewis acidities associated with ring size markedly influence the regioselectivities of the borylcupration step. Furthermore, this study reveals that the reduced steric bulk of boronate moieties, as well as diminished Lewis acidities, serve as pivotal factors contributing to internal selectivity. This provides crucial insights into the regiocontrol in the copper-catalyzed borylations of terminal alkynes.
Author Tsushima, Takumi
Nakamoto, Masaaki
Yoshida, Hiroto
AuthorAffiliation Graduate School of Advanced Science and Engineering
AuthorAffiliation_xml – name: Graduate School of Advanced Science and Engineering
Author_xml – sequence: 1
  givenname: Takumi
  surname: Tsushima
  fullname: Tsushima, Takumi
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  givenname: Masaaki
  orcidid: 0000-0002-4949-9338
  surname: Nakamoto
  fullname: Nakamoto, Masaaki
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  givenname: Hiroto
  orcidid: 0000-0001-6890-4397
  surname: Yoshida
  fullname: Yoshida, Hiroto
  email: yhiroto@hiroshima-u.ac.jp
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Keywords copper catalysis
steric properties of cyclic boronate
terminal alkynes
boron-Lewis acidity
diborons
internal selectivity
Language English
Japanese
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Snippet The installation of a boron functionality into a more substituted carbon of terminal alkynes in copper-catalyzed borylations with diborons is still a...
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Title Modulation of Lewis Acidity and Steric Parameters in Cyclic Boronates: Copper-Catalyzed Internal-Selective Borylation of Challenging Terminal Alkynes
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