Oxadendralenes in asymmetric organocatalysis for the construction of tetrahydroisochromenes

Chemical Science
Niels HammerKarl Anker Jørgensen

Abstract

Oxadendralenes are integrated in a novel manner into a one-pot cascade utilizing synergistic catalysis for the construction of valuable and complex bicyclic heterocyclic scaffolds. The construction is based on the organocatalytic activation of the oxadendralenes generating a vinylogous iminium-ion intermediate which is set-up for a 1,6-addition with an enamine formed from an aldehyde and the same organocatalyst. This reaction generates a cyclic oxadendralenic intermediate, which acts as an electron-deficient heterodiene reacting in a Lewis-acid catalyzed hetero-Diels-Alder reaction with vinyl ethers to form tetrahydroisochromenes with five continuous stereocenters in high yields, >20 : 1 dr and 99% ee. This synergistic organo- and Lewis-acid catalysed system also displays high tolerance for variation in oxadendralenes and aldehydes, which provides tetrahydroisochromenes with high diversity in the substituent pattern and the same excellent stereoselectivities. Mechanistic studies have been performed to account for the activation modes and stereochemical outcome of the reaction. The reaction concept has been extended to also include a sequential organocatalytic reaction of oxadendralenes with aldehydes, in which the enamine forme...Continue Reading

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Citations

Jun 4, 2016·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Hamish B HepburnPaolo Melchiorre
Nov 25, 2016·Chemical Society Reviews·Lydia KlierKarl Anker Jørgensen
Apr 4, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Ignacio E TobalPilar García-García

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Methods Mentioned

BETA
X-ray
acetylation

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