Zinc catalysis cycloaddition

Cycloaddition of 2-cyanoalk-2-enones with several conjugated dienes proceeded under zinc chloride catalysis.636 Zinc halides have also shown reactivity with phenylacetylenes.637 Zinc chloride is an effective Lewis acid catalyst in the Diels Alder reactions of the keto esters and the effects on stereochemistry of catalysts used have been examined.638... 

Tetrahydropyrimidines 949 are produced by the formal [4- -2] cycloaddition of A -tosylazetidines 948 with nitriles under the influence of boron trifluoride or zinc triflate catalysis <2004OL4829, 2005JA16366, 2006TL5393>. 

The first effective enantioselective 1,3-dipolar cycloaddition of diazoalkanes catalyzed by chiral Lewis acids was reported in the year 20(X) (139). Under catalysis using zinc or magnesium complexes and the chiral ligand (R,/ )-DBFOX/Ph, the reaction of diazo(trimethylsilyl)methane with 3-alkenoyl-2-oxazolidin-2-one 75 (R = H) gave the desilylated A -pyrazolines (4S,5R)-76 (R =Me 87% yield, 99% ee at 40 °C) (Scheme 8.18). Simple replacement of the oxazohdinone with the 4,4-dimethyloxazolidinone ring resulted in the formation of (4R,5S)-77 (R = Me 75% yield, 97% ee at -78 °C). 

Under appropriate conditions, even unactivated alkenes will take part in intermolecular cycloadditions with 3- and 5-bromo-2-pyrones and with 3-methoxycarbonyl-2-pyrone. Reactions can be conducted at 100 °C, or at room temperature under 10-12 kbar and with zinc chloride catalysis. 

During the last decade, use of oxazaborolidines and dioxaborolidines in enantioselective catalysis has gained importance. [1, 2] One of the earliest examples of oxazaborolidines as an enantioselective catalyst in the reduction of ketones/ketoxime ethers to secondary alco-hols/amines was reported by Itsuno et al. [3] in which (5 )-valinol was used as a chiral ligand. Since then, a number of other oxazaborolidines and dioxaborolidines have been investigated as enantioselective catalysts in a number of organic transformations viz a) reduction of ketones to alcohols, b) addition of dialkyl zinc to aldehydes, c) asymmetric allylation of aldehydes, d) Diels-Alder cycloaddition reactions, e) Mukaiyama Michael type of aldol condensations, f) cyclopropana-tion reaction of olefins. 

Furan also undergoes cycloadditions with allenes and even with simpler dienophiles, like acrylonitrile and acrylate (specifically enhanced by the presence of zinc iodide),and with maleate and fumarate esters, if the addition is conducted under high pressure. This device can also be used to increase markedly the reactivity of 2-methoxy- and 2-acetoxyfuran towards dienophiles. Lewis acid catalysis can also been used to accelerate furan Diels-Alder additions. At higher reaction temperatures alkynes and even electron-rich alkenes will add to furan. 

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