In Situ Allene Formation via Alkyne Tautomerization to Promote [4 + 2]-Cycloadditions with a Pendant Alkyne or Nitrile

Niklas Kraemer; Rajasekhar R Naredla; Thomas R. Hoye

doi:10.1021/acs.orglett.2c00491

In Situ Allene Formation via Alkyne Tautomerization to Promote [4 + 2]-Cycloadditions with a Pendant Alkyne or Nitrile

Niklas Kraemer, Rajasekhar R Naredla, Thomas R. Hoye

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

We have explored the net-[4 + 2]-cycloadditions of a variety of aryl (or alkenyl) alkynes. Tautomerization via base-catalyzed alkyne-to-allene isomerization produces a transient allene, which undergoes stepwise cyclization with not only a pendant alkyne but also a nitrile. The operative mechanisms for these reactions were studied by density functional theory and compared with the slower thermal cyclization of the precursor alkyne.

Original language	English (US)
Pages (from-to)	2327-2331
Number of pages	5
Journal	Organic Letters
Volume	24
Issue number	12
DOIs	https://doi.org/10.1021/acs.orglett.2c00491
State	Published - Apr 1 2022

Bibliographical note

Funding Information:
This research was made possible by a grant from the National Institutes of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). N.K. is supported by a Graduate Research Fellowship from the National Science Foundation. NMR spectral data were collected, in part, with an instrument funded by the NIH Shared Instrumentation Grant program (S10OD011952). High-resolution mass spectra measured at the University of Minnesota Masonic Cancer Center were done using instrumentation that was partially funded by an NIH Cancer Center Support Grant (CA-77598). Computational studies were performed using software and hardware made available by the University of Minnesota Supercomputing Institute (MSI).

Publisher Copyright:
© 2022 American Chemical Society.

Keywords

Alkadienes
Alkynes
Catalysis
Cycloaddition Reaction
Nitriles

PubMed: MeSH publication types

Journal Article
Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.

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10.1021/acs.orglett.2c00491

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title = "In Situ Allene Formation via Alkyne Tautomerization to Promote [4 + 2]-Cycloadditions with a Pendant Alkyne or Nitrile",

abstract = "We have explored the net-[4 + 2]-cycloadditions of a variety of aryl (or alkenyl) alkynes. Tautomerization via base-catalyzed alkyne-to-allene isomerization produces a transient allene, which undergoes stepwise cyclization with not only a pendant alkyne but also a nitrile. The operative mechanisms for these reactions were studied by density functional theory and compared with the slower thermal cyclization of the precursor alkyne.",

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author = "Niklas Kraemer and Naredla, {Rajasekhar R} and Hoye, {Thomas R.}",

note = "Funding Information: This research was made possible by a grant from the National Institutes of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). N.K. is supported by a Graduate Research Fellowship from the National Science Foundation. NMR spectral data were collected, in part, with an instrument funded by the NIH Shared Instrumentation Grant program (S10OD011952). High-resolution mass spectra measured at the University of Minnesota Masonic Cancer Center were done using instrumentation that was partially funded by an NIH Cancer Center Support Grant (CA-77598). Computational studies were performed using software and hardware made available by the University of Minnesota Supercomputing Institute (MSI). Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

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AU - Kraemer, Niklas

AU - Naredla, Rajasekhar R

AU - Hoye, Thomas R.

N1 - Funding Information: This research was made possible by a grant from the National Institutes of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). N.K. is supported by a Graduate Research Fellowship from the National Science Foundation. NMR spectral data were collected, in part, with an instrument funded by the NIH Shared Instrumentation Grant program (S10OD011952). High-resolution mass spectra measured at the University of Minnesota Masonic Cancer Center were done using instrumentation that was partially funded by an NIH Cancer Center Support Grant (CA-77598). Computational studies were performed using software and hardware made available by the University of Minnesota Supercomputing Institute (MSI). Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/4/1

Y1 - 2022/4/1

N2 - We have explored the net-[4 + 2]-cycloadditions of a variety of aryl (or alkenyl) alkynes. Tautomerization via base-catalyzed alkyne-to-allene isomerization produces a transient allene, which undergoes stepwise cyclization with not only a pendant alkyne but also a nitrile. The operative mechanisms for these reactions were studied by density functional theory and compared with the slower thermal cyclization of the precursor alkyne.

AB - We have explored the net-[4 + 2]-cycloadditions of a variety of aryl (or alkenyl) alkynes. Tautomerization via base-catalyzed alkyne-to-allene isomerization produces a transient allene, which undergoes stepwise cyclization with not only a pendant alkyne but also a nitrile. The operative mechanisms for these reactions were studied by density functional theory and compared with the slower thermal cyclization of the precursor alkyne.

KW - Alkadienes

KW - Alkynes

KW - Catalysis

KW - Cycloaddition Reaction

KW - Nitriles

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JO - Organic Letters

JF - Organic Letters

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ER -

In Situ Allene Formation via Alkyne Tautomerization to Promote [4 + 2]-Cycloadditions with a Pendant Alkyne or Nitrile

Abstract

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