Ethers, cyclic from alcohols

Erlenmeyer synthesis org chem Preparation of cyclic ethers by the condensation of an aldehyde with an a-acylamino acid in the presence of acetic anhydride and sodium acetate. 3r-l3n,mT-3r sin-th3-s3s erucic acid org chem C22H42O2 A monoethenoid acid that is the cis isomer of bras-sidic acid and makes up 40 to 50% of the total fatty acid in rapeseed, wallflower seed, and mustard seed crystallizes as needles from alcohol solution, insoluble in water, soluble in ethanol and methanol. o rus ik as ad erythrite See erythritol. er o.thrTt ... 

In comparison to the N- and S-counterparts, alkoxides possess lower nucleophilicity. Therefore, the reductive elimination process to form the C—O bond is much slower than those to form C— N and C—S bonds [103]. Palucki, Wolfe and Buchwald developed the first intramolecular Pd-catalyzed synthesis of cyclic aryl ethers from o-haloaryl-substituted alcohols [104]. For example, 3-(2-bromophenyl)-2-melhyl-2-butanol (91) was converted to 2,2-dimethylchroman (92) under the agency of catalytic Pd(OAc)2 in the presence (S)-(-)-2,2 -bis(di-p-tolylphosphino)-l,l -binaphthyl (Tol-BINAP) as the ligand and K2C03 as the base. The method worked well for the tertiary alcohols, moderately well for cyclic secondary alcohols, but not for acyclic secondary alcohols. 

In a similar manner, Grignard reagents react with cyclic a,/3-dihalo ethers derived from 3,4-dihydro-l,2-pyran and tetrahydrofuran to form the corresponding 2-alkyl-3-halo derivatives. Thus, addition of 2,3 dibromotetrahydropyran to methylmagnesium halide at 0° followed by hydrolysis gives a 65% yield of 2-methyl-3-bromotetrahydropyran. These materials are valuable intermediates in the synthesis of olefinic alcohols (cf. method 99). 

Attempts to attack the i4a-methyl group of lanosterol from a 9a-alkoxy-radical gave only a 9,io-seco-9-ketone [53], although the 7a-alkoxy radicai readily formed a cyclic ether with the I4a-methyl group [54]. Finally, a selection of secondary alkoxy-radicals derived from alcohols adjacent to quaternary centres e.g. la- or ij8-0H [55], 3j5-OH-4,4-dimethyl [56], 17/S-OH [36J, and 2i-OH-20-cyclic ketal [56]) gave fragmentation products which were either unsaturated carbonyl compounds, or acetoxy derivatives resulting from combination of alkyl and acetoxy radicals, e.g. ... 

To exploit the whole capacity of the Claisen rearrangement, appropriate methods for the preparation of the allyl vinyl ethers starting from allyl alcohols are necessary. The classical approach involves vinyl-ation with simple vinyl ethers or acetals. Unfortunately these methods fail with more complex systems and do not allow, except in the case of cyclic enol ethers, control of the stereochemistry of the substituted enol ether double bond. Until recently it was only possible to generate such substituted systems with appreciable stereocontrol via ketene N.O-acetals. Their preparation by addition of lyl alcohols to substituted ynamines can lead to adducts of either ( )- or (Z)-geometry, depending upon the conditions used (Scheme 60). 

Formation of an anhydride from an acid is similar to the formation of an ether from alcohols. When dicarboxylic acids are heated up to 200 - 300 °C, cyclic anhydrides with five or six carbons are formed. 

The reaction of mono- and poly-alcohols catalyzed by solid acids has been widely investigated. An important application is the synthesis of five membered cyclic ethers starting from di- or triols. Several authors described such cyclisation reactions, starting from 1,2,4-butanetriol (clay) [1], 1,2,5-pentatriol (pentasile, mordenite, erionite) [2]. Linear ethers like dimethyl ether are formed from methanol (modified aluminosilicate, zeolites) [3,4] or MTBE from methanol and i-butene (zeolite, resin) [5,6] The yields of the desired products are often quite high, e g over 90 % in the case of 1,2,4-butanetriol to 3-hydroxy-tetrahydrofiiran and about 60 % in the case of dimethyl ether. The reactions are either carried out in the presence of water as slurry process [1,2] at 150 - 200 °C or at temperatures > 300 °C in the gas phase with a fixed bed catalyst [2-4]... 

Koreeda and Hamann have reported the use of silyl tethers in stereocontrolled syntheses of branched-chain 1,4-diols and 1,5-diols [61]. Exposure of (bromomethyl)silyl ethers prepared from the corresponding homoallylic alcohols with Bu SnH in the presence of AIBN allowed smooth conversion to the corresponding cyclic siloxanes, from which diol products were obtained using standard, oxidative cleavage protocols. While monosubstituted olefin 149 selectively underwent 1-endo cyclization, di- and trisubsti-tuted olefins 150 and 151 preferentially reacted through the 6-exo mode with complete stereocontrol, affording the diol products 152 and 153, respectively (Scheme 10-50). 

In the case of peraksine [RP-5 (27)] it was shown to have the formula C19H22N2O2, a fact not readily derived from combustion analysis since the free base crystallized from alcohol in a hydrated form (27). It has also been observed that this water of solvation could be displaced by chloroform (20). Peraksine has UV-absorption typical of a 2,3-disub-stituted indole and reacted with benzoyl chloride to form an 0-benzoyl derivative. The second oxygen was apparently present as a cyclic ether when it was found that although peraksine did not react with hydrazine derivatives, it was reducible with sodium borohydride to furnish a diol (mp 290°-291° [a]j) - -41° in Py diacetate, mp 103°-105°). This diol readily lost the elements of water upon acid treatment to afford a new ether, deoxyperaksine, 230° change in crystalline form (mp 255°-257°). Because of these properties peraksine was considered to possess a cyclic hemiacetal moiety. 

Photolysis of the hypoiodites derived from alcohols (37a) and (37b) gave the aldehydes (38a) and (38b) respectively. The related alcohol (39) formed the cyclic ether (40) as well as the expected aldehyde (41) when submitted to photolysis in the presence of mercuric oxide and iodine. The synthesis of steroidal alkaloids of the c-nor-D-homo variety has been reviewed. ... 

In 2011,Jiang and co-workers showed a versatile alternative to the in situ preparation of the propargyl vinyl ethers starting from propargylic alcohols and acceptor-substituted alkynes (110BC7313).To this end, cyclic 1,3-diketones 25 and propargylic alcohols 24 were employed, and the corresponding enol ethers were obtained with iron(IIl) tosylate (Scheme 10)... 

Lead tetraacetate pyridineiirradiation Cyclic ethers and ketones from alcohols... 

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