Eliminations with zinc

By way of contrast, the Lability of the oxazolidine N, 0-acetal group is markedly enhanced by first removing the electron withdrawing carbamate group. For example. in the synthesis of FR-900482 [Scheme 8.158], Terashima and co-workers284 excised a Troc group by reductive elimination with zinc in aqueous acetic... 

The lessons learned from the abortive experiments in Scheme 12 were invaluable to Kozikowski and co-workers in developing a slate of do s and dont s for the final strategy (Scheme 13). Most notably, it transpired that the a,P-epoxy lactone C16 (c.f. C9, Scheme 12) underwent classical reductive elimination with zinc in acetic acid to give the P-hydroxy lactone C17, and cyclohexylidenation, followed by oxidation then led to the actinobolin skeleton in CIS. Final processing to give actinobolin hydrochloride now proved to be uneventful. 

Terminal alkynes react with propargylic carbonates at room temperature to afford the alka-l, 2-dien-4-yne 14 (allenylalkyne) in good yield with catalysis by Pd(0) and Cul[5], The reaction can be explained by the transmetallation of the (7-allenylpailadium methoxide 4 with copper acetylides to form the allenyKalk-ynyl)palladium 13, which undergoes reductive elimination to form the allenyl alkyne 14. In addition to propargylic carbonates, propargylic chlorides and acetates (in the presence of ZnCb) also react with terminal alkynes to afford allenylalkynes[6], Allenylalkynes are prepared by the reaction of the alkynyl-oxiranes 15 with zinc acetylides[7]. 

Many carbamates have been used as protective groups. They are arranged in this chapter in order of increasing complexity of stmcture. The most useful compounds do not necessarily have the simplest stmctures, but are /-butyl (BOC), readily cleaved by acidic hydrolysis benzyl (Cbz or Z), cleaved by catalytic hy-drogenolysis 2,4-dichlorobenzyl, stable to the acid-catalyzed hydrolysis of benzyl and /-butyl carbamates 2-(biphenylyl)isopropyl, cleaved more easily than /-butyl carbamate by dilute acetic acid 9-fluorenylmethyl, cleaved by /3-elimination with base isonicotinyl, cleaved by reduction with zinc in acetic acid 1-adamantyl, readily cleaved by trifluoroacetic acid and ally], readily cleaved by Pd-catalyzed isomerisation. 

The 10l -acetoxy group can be red actively removed with zinc and acetic acid or chromous chloride to give I9-norsteroids in high yield. Thermal elimination (boiling tetralin) of acetic acid from the crude 10)5-acetoxy-A -3-ketone or treatment with methanolic alkali leads to aromatization of ring A. Estrone alkyl ethers are formed from 10)5-acetoxy-19-nor-A -androstene-3,17-dione by treatment with alcohols and perchloric acid. Similar aromatizations are observed with 5,10-oxido, 5,10-dihydroxy, 5,10-halohydrins or 5,10-dihalo-3-ketones. ... 

These ethers can be removed from naphthohydroquinones either by elimination to the vinyl ether followed by hydrolysis or by Finklestein reaction with iodide followed by reduction with zinc. ... 

A 2.5-dibromo-7-oxabicyclo[4.1.0]hept-3-ene derivative with a hexamethylene bridge between C2 and C5 undergoes elimination of bromine to give 5 when treated with zinc.164... 

The addition of (Z)-3-(alkylamino)-2-butenoic acid esters to nitroalkenes derived from open-chain sugars gave a 50 50 mixture of diastereomeric products 32. The reaction of chiral 2-sub-stituted l-(2-nitroethenyl)pyrrolidines with zinc enolates of 3-substituted tetrahydro-2//-pyran-2-oncs in 1,2-dimethoxyethane at — 78 °C afforded the corresponding 3,3-disubstituted products in 82-96% ee via an addition-elimination process33. The stereochemical course of the reaction was determined by chemical correlation of (S)-( )-3-ethyltetrahydro-3-(2-ni-troethenyl)-2//-pyran-2-one with ( + )-quebrachamine. 

The elimination of OR and halogen from P-halo ethers is called the Boord reaction. It can be carried out with zinc, magnesium, sodium, or certain other reagents.The... 

Solutions of different carboxylic acids (fiimaric acid [FA], maleic acid, acrylic acid, succinic acid, and malonic acid) in ethanol have been effectively used as primers to increase the adhesion of synthetic vulcanized SBRs. The increase in the adhesion properties of SBR treated with carboxylic acid is attributed to the elimination of zinc stearate moieties and the deposition of acid on the rubber which migrates into the solvent-borne polyurethane adhesive layer once the adhesive joint is formed. The nature of the carboxylic acid determines the rate of diffusion into the adhesive and the extent of rubber-adhesive interfacial interaction. 

If the carbonyl group must be regenerated under nonhydrolytic conditions, (3-halo alcohols such as 3-bromopropane-l,2-diol or 2,2,2-trichloroethanol can be used for acetal formation. These groups can be removed by reduction with zinc, which leads to (3-elimination. 

The isoindolobenzazepine 380 obtained readily from prechilenine (139), 13-hydroxyoxyberberine (134), or oxybisberberine (130) (223), was recently isolated and named as chilenine (225). On reduction with zinc in hydrochloric acid-acetic acid 380 gave chilenamine (458) along with the hydroxylated product 459 (Scheme 94). Reduction of 380 followed by methylation and elimination of methanol gave pictonamine (460). On treatment with sodium hydroxide in aqueous methanol, 380 was converted to the isoindole 461, exposure of which to trifluoroacetic acid promoted cyclization and decarboxylation to afford the isoindoloisoquinoline neuvanine (462) (226). Its structure was revised (227) from the one originally proposed 463 (228). 

The success of this reaction was ascribed to the solubility of the chlorozinc intermediate, whereas other chloramine-T derivatives (e.g. the sodium salt) are insoluble. An alternative non-nitrene pathway was not eliminated from consideration. On the other hand, no aromatic substitution or addition, characteristic of a free sulphonyl nitrene (see below), took place on treatment of jV,lV-dichloromethanesulphonamides with zinc powder in benzene in the cold or on heating. The only product isolated was that of hydrogen-abstraction, methanesulphonamide 42>, which appears to be more characteristic of the behaviour of a sulphonyl nitrene-metal complex 36,37). Photolysis of iV.iV-dichloromethanesulphonamide, or dichloramine-B, or dichloramine-T in benzene solution led to the formation of some unsubstituted sulphonamide and some chlorobenzene but no product of addition of a nitrene to benzene 19>. 

They have developed direct asymmetric synthesis of quaternary carbon centers via addition-elimination process. The reactions of chiral nitroenamines with zinc enolates of a-substituted-8-lactones afford a,a-disubstituted-6-lactones with a high ee through addition-elimination process, in which (5)-(+)-2-(methoxy methy l)pyrrolidine (SMP) is used as a chiral leaving group (Eq. 4.96).119 Application of this method to other substrates such as a-substituted ketones, esters, and amides has failed to yield high ee. 

Bajic and Jaselskis [153] described a spectrophotometric method for the determination of nitrate and nitrite in seawater. It included the reduction of nitrate and nitrite to hydroxylamine by the zinc amalgam reactor (Jones reductor) at pH 3.4 and reoxidation of the product with iron (III) in the presence of ferrozine. Interference by high levels of nitrite could be eliminated with azide treatment. Levels of nitrate of 0.1 mg/1 could be detected with a precision of 3% in the presence of large amounts of nitrite and chloride. 

The elimination of impurities by cementation with zinc dust can be estimated by examining an expression of the type ... 

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