Phase transfer catalysed double carbonylation of styrene oxides

Abstract

A novel double carbonylation of styrene oxides occurs on treatment of the heterocycle with carbon monoxide, methyl iodide, NaOH (0.5 M), C6H6, CO*(CO)~ as the metal catalyst, and cetyltrimethylammonium bromide as the phase transfer agent.

Double carbonylation and beyond: systems at work and their organometallic models

“…25 Other substrates. Double carbonylation was also observed with cobalt carbonyl under conditions similar to those described above, namely with styrene oxides, 26 alkyl bromides or iodides 27 and phenetyl bromide. 28 Other results are also relevant in this context: they concern a supplementary CO insertion in a strained cyclobutanone 29 and sequential chaining of CO on acetylenic substrates.…”

Transition Metal Catalyzed Approaches to Lactones Involving CO Bond Formation

“…Transition metal catalyzed ring expansions of cyclic ethers to lactones under pressures of CO [51,52] have been reported for tetrahydrofuran [53], oxetanes, and epoxides [54][55][56]. Carbonylation of epoxides is particularly important since b-lactone products are challenging synthetic targets (see Section 2.2.5).…”

Carbonylation of Heterocycles by Homogeneous Catalysts.

“…Though b-lactone carbonylation is a high-yielding and selective route to succinic anhydrides, the one-pot, tandem carbonylation of epoxides directly to succinic anhydrides is more desirable. Prior to our serendipitous discovery of b-lactone carbonylation, double carbonylation from epoxide to succinic anhydride was unknown, although styrene oxide and aryl epoxyalcohols have been doubly 93 and triply carbonylated, 94 respectively, to other products. Unfortunately, in the case of 1, the single-pot tandem carbonylation reaction is impractical, as conditions that accelerate the first carbonylation impede the second, and vice versa.…”