Facile Preparation of tert-Butyl 1-tert-Butoxycarbonylaminocyclopent-3-enecarboxylate from Inexpensive Starting Materials

Abstract

1,5-C,C-Cycloalkylation of tert-butyl acetoacetate (1) with cis-1,4-dichloro-2-butene (2) followed by the haloform reaction of the product in NaOH solution and subsequent Curtius degradation in tert-butyl alcohol furnished tert-butyl 1-tert-butoxycarbonylaminocyclopent-3-enecarboxylate (5) in 32% overall yield.

Key words

alkenes - cyclizations - excitatory amino acids - haloform reaction - Curtius rearrangement

References

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7

tert-Butyl N-(diphenylmethylene)glycinate is commercially available at a price of 46.60 EUR per 1 g (Aldrich).

9

The price of methyl tert-butyl malonate is 45.00 EUR for 10 mL (Aldrich).

10

The price of tert-butyl acetoacetate(1) is 43.20 EUR for 500 mL (Aldrich).

11

cis-1,4-Dichloro-2-butene(2) is commercially available at a price of 133.00 EUR for 100 g (Aldrich).

13

Without tin tetrachloride, the yield was only 17%.

14

Diphenylphosphoryl azide (DPPA) is commercially available at a price of 136.35 EUR for 100 g (Aldrich) or else can easily be prepared.¹⁵