The aza-hexadehydro-diels-alder reaction

Severin K. Thompson; Thomas R. Hoye

doi:10.1021/jacs.9b11243

The aza-hexadehydro-diels-alder reaction

Severin K. Thompson, Thomas R. Hoye

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

17 Scopus citations

Abstract

The generation of pyridynes from diyne nitriles is reported. These cyano-containing precursors are analogues of the triyne substrates typically used for the hexadehydro-Diels-Alder (HDDA) cycloisomerization reactions that produce ring-fused benzynes. Hence, the new processes described represent aza-HDDA reactions. Depending on the location of the nitrile, either 3,4-pyridynes (from 1,3-diynes containing a tethered cyano group) or 2,3-pyridynes (from 1-cyanoethyne derivatives containing a tethered alkyne) are produced. In situ trapping of these reactive intermediates leads to highly substituted and functionalized pyridine derivatives. In several instances, unprecedented pyridyne trapping reactions are seen. Differences in reaction energetics between the aza-HDDA substrates and that of their analogous HDDA (triyne) substrates are discussed.

Original language	English (US)
Pages (from-to)	19575-19580
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	141
Issue number	50
DOIs	https://doi.org/10.1021/jacs.9b11243
State	Published - Dec 18 2019

Bibliographical note

Funding Information:
Support for this work was provided by the Institute of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). A portion of the NMR data was obtained with an instrument purchased with funds from the NIH Shared Instrumentation Grant program (S10OD011952). Computations were performed with resources made available by the University of Minnesota Supercomputing Institute (MSI).

Funding Information:
Support for this work was provided by the Institute of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). A portion of the NMR data was obtained with an instrument purchased with funds from the NIH Shared Instrumentation Grant program (S10OD011952). Computations were performed with resources made available by the University of Minnesota Supercomputing Institute (MSI).

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© 2019 American Chemical Society. All rights reserved.

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abstract = "The generation of pyridynes from diyne nitriles is reported. These cyano-containing precursors are analogues of the triyne substrates typically used for the hexadehydro-Diels-Alder (HDDA) cycloisomerization reactions that produce ring-fused benzynes. Hence, the new processes described represent aza-HDDA reactions. Depending on the location of the nitrile, either 3,4-pyridynes (from 1,3-diynes containing a tethered cyano group) or 2,3-pyridynes (from 1-cyanoethyne derivatives containing a tethered alkyne) are produced. In situ trapping of these reactive intermediates leads to highly substituted and functionalized pyridine derivatives. In several instances, unprecedented pyridyne trapping reactions are seen. Differences in reaction energetics between the aza-HDDA substrates and that of their analogous HDDA (triyne) substrates are discussed.",

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note = "Funding Information: Support for this work was provided by the Institute of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). A portion of the NMR data was obtained with an instrument purchased with funds from the NIH Shared Instrumentation Grant program (S10OD011952). Computations were performed with resources made available by the University of Minnesota Supercomputing Institute (MSI). Funding Information: Support for this work was provided by the Institute of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). A portion of the NMR data was obtained with an instrument purchased with funds from the NIH Shared Instrumentation Grant program (S10OD011952). Computations were performed with resources made available by the University of Minnesota Supercomputing Institute (MSI). Publisher Copyright: {\textcopyright} 2019 American Chemical Society. All rights reserved.",

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N2 - The generation of pyridynes from diyne nitriles is reported. These cyano-containing precursors are analogues of the triyne substrates typically used for the hexadehydro-Diels-Alder (HDDA) cycloisomerization reactions that produce ring-fused benzynes. Hence, the new processes described represent aza-HDDA reactions. Depending on the location of the nitrile, either 3,4-pyridynes (from 1,3-diynes containing a tethered cyano group) or 2,3-pyridynes (from 1-cyanoethyne derivatives containing a tethered alkyne) are produced. In situ trapping of these reactive intermediates leads to highly substituted and functionalized pyridine derivatives. In several instances, unprecedented pyridyne trapping reactions are seen. Differences in reaction energetics between the aza-HDDA substrates and that of their analogous HDDA (triyne) substrates are discussed.

AB - The generation of pyridynes from diyne nitriles is reported. These cyano-containing precursors are analogues of the triyne substrates typically used for the hexadehydro-Diels-Alder (HDDA) cycloisomerization reactions that produce ring-fused benzynes. Hence, the new processes described represent aza-HDDA reactions. Depending on the location of the nitrile, either 3,4-pyridynes (from 1,3-diynes containing a tethered cyano group) or 2,3-pyridynes (from 1-cyanoethyne derivatives containing a tethered alkyne) are produced. In situ trapping of these reactive intermediates leads to highly substituted and functionalized pyridine derivatives. In several instances, unprecedented pyridyne trapping reactions are seen. Differences in reaction energetics between the aza-HDDA substrates and that of their analogous HDDA (triyne) substrates are discussed.

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The aza-hexadehydro-diels-alder reaction

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