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Org Lett. 2016 Sep 16;18(18):4466-4469. doi: 10.1021/acs.orglett.6b01938. Epub 2016 Sep 6.

1,3-Dipolar Cycloaddition with Diazo Groups: Noncovalent Interactions Overwhelm Strain.

Author information

1
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin, 53706, United States.
2
Department of Biochemistry, University of Wisconsin-Madison, Madison, Wisconsin, 53706, United States.
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Contributed equally

Abstract

Like azides, diazoacetamides undergo 1,3-dipolar cycloadditions with oxanorbornadienes (OND) in a reaction that is accelerated by the relief of strain in the transition state. The cycloaddition of a diazoacetamide with unstrained ethyl 4,4,4-trifluoro-2-butynoate is, however, 35-fold faster than with the analogous OND because of favorable interactions with the fluoro groups. Its rate constant (k = 0.53 M(-1) s(-1) in methanol) is comparable to those of strain-promoted azide-cyclooctyne cycloadditions.

PMID:
27599159
PMCID:
PMC5148626
DOI:
10.1021/acs.orglett.6b01938
[Indexed for MEDLINE]
Free PMC Article

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