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Highly selective formal [3 + 2]-cycloaddition of vinyldiazoacetates with quinone ketals and quinoneimine ketals has been accomplished at room temperature with catalytic amounts of the Brønsted acid triflimide, leading to highly functionalized diazoacetates in good yields. The vinyldiazonium ion generated by electrophilic addition to the vinylogous position of the reactant vinyldiazo compound is the key intermediate in this selective transformation. Both oximidovinyldiazoacetates and those with other vinyl substituents undergo cycloaddition reactions with quinone ketals whose products, after extended reaction times, undergo substrate-dependent 1,2-migration; catalysis by Rh2(OAc)4, HNTf2, and Sc(OTf)3 effects these 1,2-migrations to the same products. However, the products from HNTf2-catalyzed reactions between quinoneimine and oximidovinyldiazoacetates undergo Rh2(OAc)4-catalyzed 1,3-C−H insertion. 1,3-Difunctionalization products are obtained for electrophilic reactions of Eschenmoser’s salt with selected vinyldiazoacetates, but with α-dibenzylaminomethyl ether, 1,6-hydride transfer reactions are observed with oximidovinyldiazoacetates.
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Elusive Arylalkylcarbenes in Solution and in Crystals: Facile 1,2-R (R = H, Ph) Migrations of 1,2,2-Triphenylethylidene
Highly reactive arylalkylcarbenes generated in solution by photolysis of their aryldiazoalkane precursors tend to undergo competing inter- and intramolecular reactions to yield a complex mixture of products. Having previously shown the use of crystals to effectively control the reactivity of arylalkylcarbenes to afford high yields of a single product, it was of interest to investigate whether the crystalline environment could also enable spectroscopic detection of these intermediates en route to photoproduct. Using 1,2,2-triphenyldiazoethane (3) as a model substrate to probe the effect of alternative reaction trajectories that yield triphenylethylene (5) by competing 1,2-H shift or 1,2-Ph migration, we report selectivities consistent with reaction from a spin-equilibrated carbene 4 in solution, while reactions in crystals primarily afford alkene 5 via a lattice-controlled 1,2-H shift. Attempts to detect 1,2,2-triphenylethylidene 4 in crystals by nanosecond laser flash photolysis or by triplet-triplet fluorescence at 77 K were unsuccessful, indicating that arylalkylcarbenes possessing α-H substituents undergo facile 1,2-H shifts both in solution and in the solid state. However, related tert-butylphenylmethylene with no α-H substituents could be observed by triplet-triplet fluorescence at 77 K in glassy matrices.
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- Award ID(s):
- 2154210
- PAR ID:
- 10633459
- Editor(s):
- NA
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 146
- Issue:
- 33
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 23221 to 23229
- Subject(s) / Keyword(s):
- solid state photochemistry, reactive intermediates, carbenes
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/jacs.4c05452
