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Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines.

ABSTRACT: Pyridyl tetrazines coordinated to metals like rhenium have been shown to be more reactive in [4 + 2] cycloadditions than their uncomplexed counterparts. Using density functional theory calculations, we found a more favorable interaction energy caused by stronger orbital interactions as the origin of this increased reactivity. Additionally, the high regioselectivity is due to a greater degree of charge stabilization in the transition state, leading to the major product.

SUBMITTER: Turlik A

PROVIDER: S-EPMC8453624 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines.

Turlik Aneta A Houk K N KN Svatunek Dennis D

The Journal of organic chemistry 20210901 18

Pyridyl tetrazines coordinated to metals like rhenium have been shown to be more reactive in [4 + 2] cycloadditions than their uncomplexed counterparts. Using density functional theory calculations, we found a more favorable interaction energy caused by stronger orbital interactions as the origin of this increased reactivity. Additionally, the high regioselectivity is due to a greater degree of charge stabilization in the transition state, leading to the major product. ...[more]

PMID: 34468143

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