TY - JOUR
T1 - An Untethered and Formal Intermolecular Hexadehydro-Diels-Alder Reaction
T2 - Alkynylboronates with 2-(1,3-Butadiynyl)pyridines
AU - Kaicharla, Trinadh
AU - Jin, Mengyuan
AU - Hoye, Thomas R.
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/12/18
Y1 - 2024/12/18
N2 - We show that 2-diynylpyridine and a Bpin-terminated monoyne or diyne will cross-react to form benzyne intermediates. These reactive intermediates are captured by various in situ trapping agents to give products of three-component reactions. Various control reactions, substrate modification, binding studies, and DFT analysis suggest that a small amount of a noncovalent Lewis acid-base complex is the active species within which the diyne and diynophile engage to produce the benzyne. Only a single isomeric benzyne is formed when a Bpin-diyne is used; this selectivity is rationalized by the geometric distortion seen in the DFT-computed diradical intermediate.
AB - We show that 2-diynylpyridine and a Bpin-terminated monoyne or diyne will cross-react to form benzyne intermediates. These reactive intermediates are captured by various in situ trapping agents to give products of three-component reactions. Various control reactions, substrate modification, binding studies, and DFT analysis suggest that a small amount of a noncovalent Lewis acid-base complex is the active species within which the diyne and diynophile engage to produce the benzyne. Only a single isomeric benzyne is formed when a Bpin-diyne is used; this selectivity is rationalized by the geometric distortion seen in the DFT-computed diradical intermediate.
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U2 - 10.1021/jacs.4c11622
DO - 10.1021/jacs.4c11622
M3 - Article
C2 - 39641921
AN - SCOPUS:85212530944
SN - 0002-7863
VL - 146
SP - 34510
EP - 34516
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 50
ER -