Electronic Character of α,3-Dehydrotoluene Intermediates Generated from Isolable Allenyne-Containing Substrates

Qian Xu; Thomas R. Hoye

doi:10.1002/anie.202207510

Electronic Character of α,3-Dehydrotoluene Intermediates Generated from Isolable Allenyne-Containing Substrates

Qian Xu, Thomas R. Hoye

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Abstract

We report here the generation of α,3-dehydrotoluenes, a relatively rare subset of reactive intermediates of the dehydroaromatic family, from isolable allenynes. The substructure motif in the allenyne substrates is distinct from, and complementary to, those found in Myers-Saito/Schmittel-type cycloisomerizations. The reactions reported here give rise to product profiles that provide insight about the electronic nature (i.e., diradical vs. zwitterion vs. cyclic allene) of the particular isomeric DHT(s) that is(are) produced under different reaction conditions differing most significantly in the polarity of the reaction solvent. One example also revealed previously unobserved carbene-like reactivity of the DHT.

Original language	English (US)
Article number	e202207510
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	40
DOIs	https://doi.org/10.1002/anie.202207510
State	Published - Oct 4 2022

Bibliographical note

Funding Information:
This research was supported by a grant from the National Institutes of General Medical Sciences (R35GM127097), a part of the U.S. Department of Health and Human Services. Some NMR spectral data were collected with an instrument partially funded by the National Institutes of Health Shared Instrumentation Grant program (S10OD011952). ESI HRMS data were obtained from the Masonic Cancer Center (Analytical Biochemistry Shared Resource laboratory) at the University of Minnesota, using instrumentation partially funded by a Cancer Center Support Grant (CA-77598). The DFT computational studies were done using resources of the University of Minnesota Supercomputing Institute (MSI).

Funding Information:
This research was supported by a grant from the National Institutes of General Medical Sciences (R35GM127097), a part of the U.S. Department of Health and Human Services. Some NMR spectral data were collected with an instrument partially funded by the National Institutes of Health Shared Instrumentation Grant program (S10OD011952). ESI HRMS data were obtained from the Masonic Cancer Center (Analytical Biochemistry Shared Resource laboratory) at the University of Minnesota, using instrumentation partially funded by a Cancer Center Support Grant (CA‐77598). The DFT computational studies were done using resources of the University of Minnesota Supercomputing Institute (MSI).

Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords

Myers-Saito cyclization
diradicals
reaction mechanisms
reactive intermediates
zwitterions

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10.1002/anie.202207510

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title = "Electronic Character of α,3-Dehydrotoluene Intermediates Generated from Isolable Allenyne-Containing Substrates",

abstract = "We report here the generation of α,3-dehydrotoluenes, a relatively rare subset of reactive intermediates of the dehydroaromatic family, from isolable allenynes. The substructure motif in the allenyne substrates is distinct from, and complementary to, those found in Myers-Saito/Schmittel-type cycloisomerizations. The reactions reported here give rise to product profiles that provide insight about the electronic nature (i.e., diradical vs. zwitterion vs. cyclic allene) of the particular isomeric DHT(s) that is(are) produced under different reaction conditions differing most significantly in the polarity of the reaction solvent. One example also revealed previously unobserved carbene-like reactivity of the DHT.",

keywords = "Myers-Saito cyclization, diradicals, reaction mechanisms, reactive intermediates, zwitterions",

author = "Qian Xu and Hoye, {Thomas R.}",

note = "Funding Information: This research was supported by a grant from the National Institutes of General Medical Sciences (R35GM127097), a part of the U.S. Department of Health and Human Services. Some NMR spectral data were collected with an instrument partially funded by the National Institutes of Health Shared Instrumentation Grant program (S10OD011952). ESI HRMS data were obtained from the Masonic Cancer Center (Analytical Biochemistry Shared Resource laboratory) at the University of Minnesota, using instrumentation partially funded by a Cancer Center Support Grant (CA-77598). The DFT computational studies were done using resources of the University of Minnesota Supercomputing Institute (MSI). Funding Information: This research was supported by a grant from the National Institutes of General Medical Sciences (R35GM127097), a part of the U.S. Department of Health and Human Services. Some NMR spectral data were collected with an instrument partially funded by the National Institutes of Health Shared Instrumentation Grant program (S10OD011952). ESI HRMS data were obtained from the Masonic Cancer Center (Analytical Biochemistry Shared Resource laboratory) at the University of Minnesota, using instrumentation partially funded by a Cancer Center Support Grant (CA‐77598). The DFT computational studies were done using resources of the University of Minnesota Supercomputing Institute (MSI). Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

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N2 - We report here the generation of α,3-dehydrotoluenes, a relatively rare subset of reactive intermediates of the dehydroaromatic family, from isolable allenynes. The substructure motif in the allenyne substrates is distinct from, and complementary to, those found in Myers-Saito/Schmittel-type cycloisomerizations. The reactions reported here give rise to product profiles that provide insight about the electronic nature (i.e., diradical vs. zwitterion vs. cyclic allene) of the particular isomeric DHT(s) that is(are) produced under different reaction conditions differing most significantly in the polarity of the reaction solvent. One example also revealed previously unobserved carbene-like reactivity of the DHT.

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Electronic Character of α,3-Dehydrotoluene Intermediates Generated from Isolable Allenyne-Containing Substrates

Abstract

Bibliographical note

Keywords

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