Ethers absolute configuration

Synthesis. In the syntheses of T and its congeners, formation of the stericaHy hindered diaryl ether core is difficult, as is the introduction of the alanyl side chain (or the preservation of its L (3) absolute configuration) and iodination to the desired degree (T or T. ... 

The homology between 22 and 21 is obviously very close. After lithium aluminum hydride reduction of the ethoxycarbonyl function in 22, oxidation of the resultant primary alcohol with PCC furnishes aldehyde 34. Subjection of 34 to sequential carbonyl addition, oxidation, and deprotection reactions then provides ketone 21 (31% overall yield from (—)-33). By virtue of its symmetry, the dextrorotatory monobenzyl ether, (/ )-(+)-33, can also be converted to compound 21, with the same absolute configuration as that derived from (S)-(-)-33, by using a synthetic route that differs only slightly from the one already described. 

Chiral dendrimers based on oligonaphthyl cores and Fr chet-type poly(aryl ether) dendrons have been investigated [44]. The absolute configuration of these dendrimers remains the same as that of their chiral cores. Both the nature of the core and the generation play a role in determining the fluorescence quantum yield. 

Further examination of the extracts of A. cannabina revealed axisonitrile-4 (7), axisothiocyanate-4 (8) and axamide-4 (9) [33], A vinylic isonitrile function was supported by H NMR signals at <51.67 and 1.89, which were assigned to the two isopropylidene methyls of 7. Difficulty in isolating the natural product 9 was circumvented, when isonitrile 7 was transformed to 9, mp 81-84 °C, by acetic acid in anhydrous ether. The absolute configurations of both axanes 1 and 7 and their analogs were later established [31] by studies including X-ray diffraction of the p-bromoaniline derivative of 2 and by CD data of ( + )-10-methyldecalone-l obtained from ozonolysis of the reduction (Na/NH3) product of 1 [1]. 

Hex- and hept-2-en-4-yn-l-ol gave hexa-3,4-dienol and hepta-3,4-dienol, respectively. The absolute configuration of ( + )-hexa-3,4-dienol was determined to be S by thermal conversion of (- )-(S)-a-chloroethyl l-methylprop-2-ynyl ether (18) to an allenic aldehyde 19, which was reduced with LAH to (+ )-hexa-3,4-dienol (17, R = Me). (See Scheme 2.)... 

An improved procedure for the synthesis of a-allenic alcohols in good yields and with approximately 90% e.e. was reported by Olsson and Claesson (56). (- )-(S)-3-Butyne-2-ol (25) was converted into the monotetrahydropyranyl derivatives 26a to c, which gave on reduction with LAH in ether or THF the chiral allenes 27a to c (Scheme 4). The absolute configurations of 27b and c were... 

The reduction of phenyl mesityl ketone was studied with LAH modified with amino alcohols 65 to 72 in ether (the ratio LAH alcohol ketone = 1.1 1.1 1) (83). Optical yields were modest, with the highest 39%, obtained with 65 as the chiral auxiliary reagent. It was observed that there is a relationship between the preferred enantiomeric product and the structure and absolute configuration of the carbons carrying the hydroxy and amino groups. Thus the threo... 

On the basis of this empirical relationship, the absolute configuration of the dextrorotatory alcohols formed in the reduction of a series of aryl alkyl ketones (75) with (—)-quinine-LAH in ether was assigned as R (84). Reduction of a series of a,p-unsaturated ketones (76) with (- )-quinine-LAH gave a product mixture consisting mainly of dextrorotatory unsaturated alcohols (77) (85). The unsaturated alcohols 77 were shown to have the R configuration. 

Diacetylhexahydromarmesin 276 has been converted into the ortho-rearranged product 277 in 30.6% yield among other photoproducts. Transformation of 277 into methyl hexahydrorutaretin methyl ether 278 served to determine the absolute configuration of rutaretin methyl ether (279) (Scheme 70) [199]. 

An elegant asymmetric synthesis of frawi-l-(2-hydroxyaryl)-2-trimethylsilylcyclo-propanes 497 of unknown absolute configuration from 2-bromoaryl ethers 496, involving... 

Simultaneous deprotection and cyclization of diols 60a and 60b with 3 M HCl in MeOH followed by acetylation yielded the 2,3-trans- ( 50%) (61a and 61b) and for the first time 2,3-cw-flavan-3-ol methylether acetate derivatives ( 20%) (62a and 62b) in excellent enantiomeric excesses (>99%). The optical purity was assessed by H NMR using [Eu(hfc)3] as chiral shift reagent. The absolute configuration of the derivatives of the tram- and cii-flavan-3-ol derivatives was assigned by comparison of CD data with those of authentic samples in the catechin or epicatechin series flavan-3-ols. Thus, the absolute configuration of the flavan-3-ol methyl ether acetates confirms the assigned configuration of the diols as derived from the Sharpless model. 

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