CuI-Mediated Bromoalkynylation and Hydroalkynylation Reactions of Unsymmetrical Benzynes: Complementary Modes of Addition

Xiao Xiao, Tao Wang, Feng Xu, Thomas R. Hoye

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Abstract

Benzynes formed by heating a suitable triyne (or tetrayne) substrate are shown to react with in situ generated alkynyl copper species. The latter are compatible with the polyyne substrates and two types of chemistries have been achieved: (i) 1-bromo-1-alkynes efficiently undergo net bromoalkynylation of the (unsymmetrical) benzynes and (ii) in situ generated alkynylcopper species give rise to hydroalkynylation products. The regiochemical preferences of these two modes of reaction are complementary to one another with respect to the position of alkynyl substituent in the final products.

Original languageEnglish (US)
Pages (from-to)16564-16568
Number of pages5
JournalAngewandte Chemie - International Edition
Volume57
Issue number50
DOIs
StatePublished - Dec 10 2018

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Alkynes
Substrates
Copper
Heating

Keywords

  • alkynylations
  • aryne trapping
  • copper
  • homogeneous catalysis

Cite this

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abstract = "Benzynes formed by heating a suitable triyne (or tetrayne) substrate are shown to react with in situ generated alkynyl copper species. The latter are compatible with the polyyne substrates and two types of chemistries have been achieved: (i) 1-bromo-1-alkynes efficiently undergo net bromoalkynylation of the (unsymmetrical) benzynes and (ii) in situ generated alkynylcopper species give rise to hydroalkynylation products. The regiochemical preferences of these two modes of reaction are complementary to one another with respect to the position of alkynyl substituent in the final products.",
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T1 - CuI-Mediated Bromoalkynylation and Hydroalkynylation Reactions of Unsymmetrical Benzynes

T2 - Complementary Modes of Addition

AU - Xiao, Xiao

AU - Wang, Tao

AU - Xu, Feng

AU - Hoye, Thomas R.

PY - 2018/12/10

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N2 - Benzynes formed by heating a suitable triyne (or tetrayne) substrate are shown to react with in situ generated alkynyl copper species. The latter are compatible with the polyyne substrates and two types of chemistries have been achieved: (i) 1-bromo-1-alkynes efficiently undergo net bromoalkynylation of the (unsymmetrical) benzynes and (ii) in situ generated alkynylcopper species give rise to hydroalkynylation products. The regiochemical preferences of these two modes of reaction are complementary to one another with respect to the position of alkynyl substituent in the final products.

AB - Benzynes formed by heating a suitable triyne (or tetrayne) substrate are shown to react with in situ generated alkynyl copper species. The latter are compatible with the polyyne substrates and two types of chemistries have been achieved: (i) 1-bromo-1-alkynes efficiently undergo net bromoalkynylation of the (unsymmetrical) benzynes and (ii) in situ generated alkynylcopper species give rise to hydroalkynylation products. The regiochemical preferences of these two modes of reaction are complementary to one another with respect to the position of alkynyl substituent in the final products.

KW - alkynylations

KW - aryne trapping

KW - copper

KW - homogeneous catalysis

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