Access to a diverse array of bridged benzo[1,5]oxazocine and benzo[1,4]diazepine structures

Grant J. Sherborne; Coura Diène; Paul Kemmitt; Andrew D. Smith

doi:10.1021/acs.orglett.3c03392

Access to a diverse array of bridged benzo[1,5]oxazocine and benzo[1,4]diazepine structures

Grant J. Sherborne^*, Coura Diène, Paul Kemmitt, Andrew D. Smith

^*Corresponding author for this work

School of Chemistry

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

Abstract

The preparation of bridged benzo[1,5]oxazocines and benzo[1,4]diazepines is demonstrated from simple aniline and aldehyde starting materials. A one-pot condensation/6π electrocyclization is followed by an intramolecular trapping of the 2,3-dihydroquinoline intermediate by nitrogen or oxygen nucleophiles to give bridged seven- and eight-membered products. Using 3-hydroxypyridinecarboxaldehydes results in a stable zwitterionic structure that can undergo a diastereoselective reduction under hydrogenative conditions. A similar cyclization/hydrogenation pathway with excellent diastereoselectivity is also demonstrated from 2-pyridyl-substituted 1,2,3,4-tetrahydroquinolines.

Original language	English
Journal	Organic Letters
Volume	Articles ASAP
Early online date	23 Nov 2023
DOIs	https://doi.org/10.1021/acs.orglett.3c03392
Publication status	E-pub ahead of print - 23 Nov 2023

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10.1021/acs.orglett.3c03392

Sherborne_2023_OL_DiverseArray_AAM
Copyright © 2023 the Authors. This work has been made available online in accordance with the University of St Andrews Open Access policy. This accepted manuscript is distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. The final published version of this work is available at https://doi.org/10.1021/acs.orglett.3c03392
Accepted author manuscript, 1.05 MBLicence: CC BY

CCDC 2277416: Experimental Crystal Structure Determination
Sherborne, G. J. (Creator), Diène, C. (Creator), Kemmitt, P. (Creator) & Smith, A. D. (Creator), Cambridge Crystallographic Data Centre, 2023
DOI: 10.5517/ccdc.csd.cc2gfv1t
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title = "Access to a diverse array of bridged benzo[1,5]oxazocine and benzo[1,4]diazepine structures",

abstract = "The preparation of bridged benzo[1,5]oxazocines and benzo[1,4]diazepines is demonstrated from simple aniline and aldehyde starting materials. A one-pot condensation/6π electrocyclization is followed by an intramolecular trapping of the 2,3-dihydroquinoline intermediate by nitrogen or oxygen nucleophiles to give bridged seven- and eight-membered products. Using 3-hydroxypyridinecarboxaldehydes results in a stable zwitterionic structure that can undergo a diastereoselective reduction under hydrogenative conditions. A similar cyclization/hydrogenation pathway with excellent diastereoselectivity is also demonstrated from 2-pyridyl-substituted 1,2,3,4-tetrahydroquinolines.",

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T1 - Access to a diverse array of bridged benzo[1,5]oxazocine and benzo[1,4]diazepine structures

AU - Sherborne, Grant J.

AU - Diène, Coura

AU - Kemmitt, Paul

AU - Smith, Andrew D.

PY - 2023/11/23

Y1 - 2023/11/23

N2 - The preparation of bridged benzo[1,5]oxazocines and benzo[1,4]diazepines is demonstrated from simple aniline and aldehyde starting materials. A one-pot condensation/6π electrocyclization is followed by an intramolecular trapping of the 2,3-dihydroquinoline intermediate by nitrogen or oxygen nucleophiles to give bridged seven- and eight-membered products. Using 3-hydroxypyridinecarboxaldehydes results in a stable zwitterionic structure that can undergo a diastereoselective reduction under hydrogenative conditions. A similar cyclization/hydrogenation pathway with excellent diastereoselectivity is also demonstrated from 2-pyridyl-substituted 1,2,3,4-tetrahydroquinolines.

AB - The preparation of bridged benzo[1,5]oxazocines and benzo[1,4]diazepines is demonstrated from simple aniline and aldehyde starting materials. A one-pot condensation/6π electrocyclization is followed by an intramolecular trapping of the 2,3-dihydroquinoline intermediate by nitrogen or oxygen nucleophiles to give bridged seven- and eight-membered products. Using 3-hydroxypyridinecarboxaldehydes results in a stable zwitterionic structure that can undergo a diastereoselective reduction under hydrogenative conditions. A similar cyclization/hydrogenation pathway with excellent diastereoselectivity is also demonstrated from 2-pyridyl-substituted 1,2,3,4-tetrahydroquinolines.

U2 - 10.1021/acs.orglett.3c03392

DO - 10.1021/acs.orglett.3c03392

M3 - Article

SN - 1523-7060

VL - Articles ASAP

JO - Organic Letters

JF - Organic Letters

ER -

Access to a diverse array of bridged benzo[1,5]oxazocine and benzo[1,4]diazepine structures

Abstract

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CCDC 2277416: Experimental Crystal Structure Determination

Cite this