Efficient Synthesis of β-Oxoalkyl Carbamates from Carbon Dioxide, Internal Propargylic Alcohols, and Secondary Amines Catalyzed by Silver Salts and DBU

Abstract

The three-component reaction of internal propargylic alcohols with secondary amines and carbon dioxide proceeded smoothly in the presence of a catalyst system comprising a silver salt and 1,8-diazabicyclo[5.4.0]undec-7-ene in 1,4-dioxane at 90 ˚C to give the corresponding β-oxoalkyl carbamates in good to high yields. The counterion of the silver salt had little effect on the reaction whereas the nature of the organic base had a marked influence.

Key words

amines - carbamates - carbon dioxide - catalysis - propargylic alcohols

References

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11

(4Z)-4-Benzylidene-1,3-dioxaspiro[4.5]decan-2-one could be quantitatively transformed into 3a by treatment with Et₂NH (1 equiv) in 1,4-dioxane at 90 ˚C for 15 h.

12

When a primary amine(butylamine) was used under the same conditions, 4-benzylidene-3-butyl-1-oxa-3-azaspiro[4.4]nonan-2-one was obtained in 81% yield (E/Z = 52:48).