Benzylic ketals

It is interesting to note that among initiators studied, a benzyl ketal type initiator (2,2-dimethoxy-2-phenyl acetophenone) is more active than other initiators of acetophenone type. 2,2-Dimethoxy-2-phenyl acetophenone is more active than BME, probably due to the presence of the extra methoxy group on the -carbon, which gives a more active phenyldimethoxy methyl radical (and it further cleaves to give an even more active methyl radical) than the phenylmethoxy methyl radical from BME (4). It is known that the phenylmethoxy methyl radical dimerizes easily and thus loses some of its role as a radical in a... 

Similar photolytic reactions occur with benzoin (VIII), benzyl ketals (IX), aroylpho-sphine oxides (X), and a-aminoalkylphenones (XI). These and related compounds are used... 

Sodium in liquid ammonia, often with alcohols as cosolvents, provides a less vigorous reducing system for benzylic alcohols. Terminal and disubstituted alkenes are reduced by the Li/NHa system, while only terminal alkenes usually succumb to Na/NHa, allowing benzylic alcohols containing unsaturation to be effectively reduced with the latter reagent. Benzylic ketals are readily reduced to hydrocarbons without overreduction using Na/NHa/alcohol (equation 70). Lithium in ammonia can lead to overreduction. 

Esoicure . [Sartomer] Benzyl ketal or benzdn ethers photoinitiators fmr composites, coatings, inks, photqx>lymers, electronic photoresists. 

The cleavage proceeds by initial reduction of the nitro groups followed by acid-catalyzed cleavage. The DNB group can be cleaved in the presence of allyl, benzyl, tetrahydropyranyl, methoxy ethoxy methyl, methoxymethyl, silyl, trityl, and ketal protective groups. 

Esters and amides are quite resistant to hydrogenation under almost all conditions so their presence is not expected to cause difficulties. Alkyl ethers and ketals are generally resistant to hydrogenolysis but benzyl ethers are readily cleaved, particularly over palladium or Raney nickel catalysts. ... 

MeOH, reagent prepared by heating Bu2SnO and Bu3SnP04, heat 2 h, 90% yield." This method is effective for primary, secondary, tertiary, benzylic, and allylic THP derivatives. The MEM group and ketals are inert to this reagent, but TMS and TBDMS ethers are cleaved. 

The general features of the monensin synthesis conducted by Kishi et al. are outlined, in retrosynthetic format, in Scheme 1. It was decided to delay the construction of monensin s spiroketal substructure, the l,6-dioxaspiro[4.5]decane framework, to a very late stage in the synthesis (see Scheme 1). It seemed reasonable to expect that exposure of the keto triol resulting from the hydrogen-olysis of the C-5 benzyl ether in 2 to an acidic medium could, under equilibrating conditions, result in the formation of the spiroketal in 1. This proposition was based on the reasonable assumption that the configuration of the spiroketal carbon (C-9) in monensin corresponds to the thermodynamically most stable form, as is the case for most spiroketal-containing natural products.19 Spiro-ketals found in nature usually adopt conformations in which steric effects are minimized and anomeric effects are maximized. 

The C2-symmetric epoxide 23 (Scheme 7) reacts smoothly with carbon nucleophiles. For example, treatment of 23 with lithium dimethylcuprate proceeds with inversion of configuration, resulting in the formation of alcohol 28. An important consequence of the C2 symmetry of 23 is that the attack of the organometallic reagent upon either one of the two epoxide carbons produces the same product. After simultaneous hydrogenolysis of the two benzyl ethers in 28, protection of the 1,2-diol as an acetonide ring can be easily achieved by the use of 2,2-dimethoxypropane and camphor-sulfonic acid (CSA). It is necessary to briefly expose the crude product from the latter reaction to methanol and CSA so that the mixed acyclic ketal can be cleaved (see 29—>30). Oxidation of alcohol 30 with pyridinium chlorochromate (PCC) provides alde-... 

Scheme 27).43b A regiospecific monohydroboration of enyne 107 with disiamylborane furnishes (A)-vinylborane 108, a substance that combines stereospecifically with vinyl iodide 109 under the indicated conditions to give conjugated triene 110 (52% overall yield). Trisporol B benzyl ether (111) is obtained after acid-induced hydrolysis of the dioxolane ketal functions.

Alkyl esters are efficiently dealkylated to trimethylsilyl esters with high concentrations of iodotrimethylsilane either in chloroform or sulfolane solutions at 25-80° or without solvent at 100-110°.Hydrolysis of the trimethylsilyl esters serves to release the carboxylic acid. Amines may be recovered from O-methyl, O-ethyl, and O-benzyl carbamates after reaction with iodotrimethylsilane in chloroform or sulfolane at 50—60° and subsequent methanolysis. The conversion of dimethyl, diethyl, and ethylene acetals and ketals to the parent aldehydes and ketones under aprotic conditions has been accomplished with this reagent. The reactions of alcohols (or the corresponding trimethylsilyl ethers) and aldehydes with iodotrimethylsilane give alkyl iodides and a-iodosilyl ethers,respectively. lodomethyl methyl ether is obtained from cleavage of dimethoxymethane with iodotrimethylsilane. 

As expected, other enol ethers work well in these procedures. For example, Jones and Selenski find that implementation of method F, which occurs by addition of MeMgBr to benzaldehyde 5 in the presence of dihydropyran (DHP) at 78 °C affords a 66% yield of the corresponding tricyclic ketal 59 with better than 50 1 endo diastereoselectivity (Fig. 4.31).27 On the contrary, Lindsey reports use of method H with the benzyl alcohol 35 and diethylketene acetal. The cycloaddition reaction occurs almost instantaneously upon deprotonation of the benzyl alcohol 35 by f-butyl-magnesium bromide in the presence of the ketene acetal and yields the corresponding benzopyran ortho ester 60 in a 67% yield.29... 

Selective removal of the benzyl ether-protecting group without hydrogenolysis of the ketal C-O bonds was performed on Ra-Ni in EtOH.154 155 A solution of benzyloxy acetal in MeOH with 5% Pd/C was stirred at room temperature with a H2 pressure from a balloon until the reaction was complete (Scheme 4.30).156... 

Because carbohydrates are so frequently used as substrates in kinetic studies of enzymes and metabolic pathways, we refer the reader to the following topics in Ro-byt s excellent account of chemical reactions used to modify carbohydrates formation of carbohydrate esters, pp. 77-81 sulfonic acid esters, pp. 81-83 ethers [methyl, p. 83 trityl, pp. 83-84 benzyl, pp. 84-85 trialkyl silyl, p. 85] acetals and ketals, pp. 85-92 modifications at C-1 [reduction of aldehydes and ketones, pp. 92-93 reduction of thioacetals, p. 93 oxidation, pp. 93-94 chain elongation, pp. 94-98 chain length reduction, pp. 98-99 substitution at the reducing carbon atom, pp. 99-103 formation of gycosides, pp. 103-105 formation of glycosidic linkages between monosaccharide residues, 105-108] modifications at C-2, pp. 108-113 modifications at C-3, pp. 113-120 modifications at C-4, pp. 121-124 modifications at C-5, pp. 125-128 modifications at C-6 in hexopy-ranoses, pp. 128-134. 

A special case of functionalized aryllithium reagents appears when the corresponding aryl group bears a ketal moiety at the benzylic position due to the lability of the benzyUc carbon-oxygen bonds. However, working under Barbier-type conditions and using naphthalene (10%) as the electron carrier catalyst, the reaction of chlorinated materials 242 afforded, after hydrolysis with water, the corresponding polyfunctionalized products 243 (Scheme 81). ... 

D. 1,4-Di-O-benzyl-L-threitol. The crude ketal is dissolved in methanol (300 mL), 0.5 N hydrochloric acid (30 idL) is added, and the resulting mixture Is heated to reflux. Acetone and methanol are slowly distilled off (Note 29). Additional methanol (50 mL) and 0.5 N hydrochloric acid (20 mL) are added and the mixture Is kept at room temperature until ketal hydrolysis Is complete. The mixture Is diluted with saturated sodium bicarbonate solution (500 mL) and extracted with ether (3 x 500 mL). The ether extracts are combined, dried over anhydrous magnesium sulfate, and filtered. Removal of volatile material under reduced pressure gives crude l,4-di-0-benzy1-L-threitol as a pale yellow solid. This solid is recrystallized twice from chloroform/hexanes, to provide 59-65 g (195-215 mmol, 57-63% yield) of pure diol, up 54-55 C (Notes 30 and 31). Concentration of the mother liquors from the recrystallizations gives a yellow solid which is chromatographed on 70-230 mesh silica gel 60 (500 g) (Note 32), and eluted with 50% ethyl... 

Homochiral molecules readily available from inexpensive sources are useful synthetic building blocks and chiral auxiliaries. 1,4-01-0-benzyl-L-threitol has been used in construction of homochiral crown ethers that are useful as enzyme model systems. Topologically controlled diastereoselective delivery of the Simmons-Smith reagent for 2-cycloalken-l-one 1,4-d1-0-benzyl-L-threitol ketals was recently reported. ... 

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