A Rapid Aza-Bicycle Synthesis from Dendralenes and Imines

Yi Min Fan; Josemon George; Jiao Yu J. Wang; Michael G. Gardiner; Michelle L. Coote; Michael S. Sherburn

doi:10.1021/acs.orglett.3c02890

A Rapid Aza-Bicycle Synthesis from Dendralenes and Imines

Yi Min Fan, Josemon George, Jiao Yu J. Wang, Michael G. Gardiner, Michelle L. Coote, Michael S. Sherburn

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

2 Citations (Scopus)

Abstract

The diene-transmissive 2-fold Diels-Alder sequence between carbon-based dienophiles and [3]dendralenes is becoming an established method for polycarbocycle synthesis. Here, we demonstrate for the first time that imines are competent participants in intermolecular formal [4 + 2] cycloadditions with dendralenes. After a second Diels-Alder process with a carbadienophile, hexahydro- and octahydro-isoquinoline structures are formed. The formal aza-Diels-Alder reaction, which requires Lewis acid promotion, proceeds in high regio- and stereoselectivity under optimized conditions. ωB97XD/Def2-TZVP//M06-2X/6-31+G(d,p) calculations reveal a stepwise ionic mechanism for the formal aza-dienophile cycloadditions and also explain an unexpected Z → E olefin isomerization of a non-reacting C═C bond in the first formal cycloaddition.

Original language	English
Pages (from-to)	7545-7550
Number of pages	6
Journal	Organic Letters
Volume	25
Issue number	41
DOIs	https://doi.org/10.1021/acs.orglett.3c02890
Publication status	Published - 20 Oct 2023

Keywords

Aza-Bicycle Synthesis
Dendralenes
Imines
diene-transmissive
Diels-Alder
Carbon-based polymer composites
dienophiles
polycarbocycle synthesis

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title = "A Rapid Aza-Bicycle Synthesis from Dendralenes and Imines",

abstract = "The diene-transmissive 2-fold Diels-Alder sequence between carbon-based dienophiles and [3]dendralenes is becoming an established method for polycarbocycle synthesis. Here, we demonstrate for the first time that imines are competent participants in intermolecular formal [4 + 2] cycloadditions with dendralenes. After a second Diels-Alder process with a carbadienophile, hexahydro- and octahydro-isoquinoline structures are formed. The formal aza-Diels-Alder reaction, which requires Lewis acid promotion, proceeds in high regio- and stereoselectivity under optimized conditions. ωB97XD/Def2-TZVP//M06-2X/6-31+G(d,p) calculations reveal a stepwise ionic mechanism for the formal aza-dienophile cycloadditions and also explain an unexpected Z → E olefin isomerization of a non-reacting C═C bond in the first formal cycloaddition.",

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AU - Fan, Yi Min

AU - George, Josemon

AU - Wang, Jiao Yu J.

AU - Gardiner, Michael G.

AU - Coote, Michelle L.

AU - Sherburn, Michael S.

PY - 2023/10/20

Y1 - 2023/10/20

N2 - The diene-transmissive 2-fold Diels-Alder sequence between carbon-based dienophiles and [3]dendralenes is becoming an established method for polycarbocycle synthesis. Here, we demonstrate for the first time that imines are competent participants in intermolecular formal [4 + 2] cycloadditions with dendralenes. After a second Diels-Alder process with a carbadienophile, hexahydro- and octahydro-isoquinoline structures are formed. The formal aza-Diels-Alder reaction, which requires Lewis acid promotion, proceeds in high regio- and stereoselectivity under optimized conditions. ωB97XD/Def2-TZVP//M06-2X/6-31+G(d,p) calculations reveal a stepwise ionic mechanism for the formal aza-dienophile cycloadditions and also explain an unexpected Z → E olefin isomerization of a non-reacting C═C bond in the first formal cycloaddition.

AB - The diene-transmissive 2-fold Diels-Alder sequence between carbon-based dienophiles and [3]dendralenes is becoming an established method for polycarbocycle synthesis. Here, we demonstrate for the first time that imines are competent participants in intermolecular formal [4 + 2] cycloadditions with dendralenes. After a second Diels-Alder process with a carbadienophile, hexahydro- and octahydro-isoquinoline structures are formed. The formal aza-Diels-Alder reaction, which requires Lewis acid promotion, proceeds in high regio- and stereoselectivity under optimized conditions. ωB97XD/Def2-TZVP//M06-2X/6-31+G(d,p) calculations reveal a stepwise ionic mechanism for the formal aza-dienophile cycloadditions and also explain an unexpected Z → E olefin isomerization of a non-reacting C═C bond in the first formal cycloaddition.

KW - Aza-Bicycle Synthesis

KW - Dendralenes

KW - Imines

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KW - Diels-Alder

KW - Carbon-based polymer composites

KW - dienophiles

KW - polycarbocycle synthesis

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A Rapid Aza-Bicycle Synthesis from Dendralenes and Imines

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