1.2- Dimesylates

Finally the dimesyl derivative (7) was prepared in a similar manner. When it reacted with azide ion, configurational inversions were observed at positions 1, 2, and 3 (formula 7), owing in part to the anchimeric effect of the position 3 acetoxy group. The vibo or dl (145/23) configuration (same as in the starting material) was retained in the final product 10 (Y = NHAc), a derivative of 3,5-diamino-l,2,4-cyclo-hexanetriol (42). 

A second crystallization from dichloromethane-pentane is sometimes necessary to achieve material having this melting point. Styrene glycol dimesylate must be stored in a refrigerator, since slow decomposition takes place at room temperature. 

The lead tetraacetate reaction between jV-aminophthalimide and (E) stilbene was first described by Rees,5 and the hydrazinolysis of the addition product by Carpino.6 The procedures described here incorporate their methods, with improvements. The dimesylate-hydrazine reaction was first described by Paulsen7 in the carbohydrate series. 

Styrene glycol dimesylate [ 1,2-Ethanediol, 1-phenyl-, dimethylsulfonate], 55,... 

CN N,N-dimethyl-10-[3-(4-methyl-1 -piperazinyl)propyI]-10/f-phenothiazine-2-sulfonamide dimesylate... 

In an earlier study the authors proposed a [3.2.0] bicyclic sulfonium salt 8 as the reactive intermediate in the trimethylsilyl iodide mediated ring contraction of 4-methoxythiephane <1996T5989>. Enantiomerically pure thio-lane derivatives were synthesized via a ring contraction of a seven-membered sulfur heterocycle by nucleophilic transannular substitution <2000TA1389>. The thiepane derivative 15, derived from d-sorbitol, was converted into the dimesyl derivative 16 following deprotection under acidic conditions. Treatment of 16 with sodium azide in DMSO at 120°C yielded the corresponding thiolane as a mixture of two diastereoisomers, 17a and 17b, in a 5 1 ratio (see Scheme 1). 

Stereospecific contraction of the seven-membered nucleus was observed on treatment of the dimesylated thiepanetetrol derivatives 67 (obtained in turn from d-sorbitol) with sodium azide to give a 5 1 mixture of the bis(azido)tetrahydrothiophenes 68 and 69. Intramolecular nucleophilic displacement of either mesylate group initiates this ring contraction <00TA1389>. 

The group of Salzer has recently reported phospholanes 54-56 based on chiral half-sandwich complexes [79]. These were obtained by treatment of the appropriately substituted complex with a secondary phospholane, itself accessed via the cyclic sulfate or dimesylate and PH3. These were tested against a range of substrates with C=C, C=0 and C=N bonds, with variable results [80]. 

Biederman J, Krishnan S, Zhang Y, McGough JJ, Findling RL. (2007) Efficacy and tolerability of lisdexamfetamine dimesylate (NRP-104) in children with attention-deficit/hyperactivity disorder A Phase 111, multicenter, randomized, double-blind, forced-dose, parallel-group study. Clin Ther 29 450 63. 

Jasinski DR, Krishnan S. (2009) Human pharmacology of intravenous lisdexamfetamine dimesylate Abuse liability in adult stimulant abusers. J Psychopharmacol 23 410-418. 

A series of polyphosphites, polyphosphates, polythiophosphates, and other polymers containing sulfone functions, based on 1, have also been described [17,119]. An efficient synthesis of polyethers from 1 and 1,8-dibromo or dimesyl octane by microwave-assisted phase transfer catalysis has been reported [120]. 

A synthesis of a dimethyl derivative of 501 has also recently been announced by Hirao, et al. Following conversion of 513 to its dimesylate, Lewis acid-catalyzed rearrangement gave dienedione 514 as the major product. Heating of the disemi-carbazone of 514 with powdered KOH furnished the diolefin which was transformed into 515 by ozonolysis. When the ditosylhydrazone of 515 was heated with potassium... 

The a-D-lyxo epoxide [232, R = (3-deoxy-l,2 5,6-di-0-isopropylidene-a-D-glucofuranose-3-yl), R1 = CH2OH] was converted into a 3,4-unsat-urated D-threo-2,6-diol (268), which was dimesylated and the diester treated with sodium azide. Two diazides (673a and 673b) were obtained and separated the latter was hydrogenated in the presence of platinum catalyst and the product acetylated, to furnish 673c. 

The parent l,4-dihydro-l,4-diazocine (232) and a number of AT,AT-derivatives have been prepared and thoroughly characterized by Prinzbach and Vogel and their colleagues (79AG(E)962, 964, 80CB3161). The benzene diimine precursors have been obtained by two routes. In one case cis benzene dioxide was converted in several steps to the mesyl derivative (225) and thence to the diimine dimesylate. The second proceeds from cis,cis- benzene trioxide to the triimine (227). Two equivalents of acid chloride give the diamides (228) in good yield, and nitrosation with cheletropic elimination of N2O leads to the N,AT -disub-stituted diimines (229). 

A solution of LiPPh2 [prepared from chlorodiphenylphosphine (3.89 g, 17.6 mmol) and Li (0.74 g, 106 mmol)] was added with stirring to a solution of 1,3-dimesylate (1.69 g, 4.4 mmol) in 30 ml THF at —20 °C. The resulting solution was allowed to warm to room temperature (5 h) and then the solvent was removed under reduced pressure. The residue was washed with MeOH (30 mL) and recrystallized from MeOH-CH2Cl2 (4 1 mixture) to afford the product as white crystals (1.34 g, 54% yield). 

Sodium toluene dispersion of, 55, 65 Sodium p-toluenesulfinate, 57, 103 Spiro[4 n] alkenones, 58, 62 Spiro[cyclopentane-l,l -indene] 55, 94 Squalene, 56, 116 Squalene, 2,3-epoxy, 56, 116 Stannic chloride, 56, 97 Steroids synthesis, 58, 85 E Stilbene, 55, 115,58, 73 z-Stilbene, 58, 133 Styrene, 56, 35,58, 43 Styrene glycol, 55, 116 Styrene glycol dimesylate, 55, 116 Succinic acid, 58, 85 Succinic anhydride, 58, 85 Sucunimide, 56, 50, 58, 126 Succimmide, Vbromo, 55, 28, 56, 49 SULFIDE CONTRACTION, 55, 127 Sulfide, dimethyl-, 56, 37 SULFIDE SYNTHESIS, 58, 143,58, 138 SULFIDE SYNTHESIS ALKYL ARYL SULFIDES, 58, 143 SULFIDE SYNTHFSIS DIALKYL SULFIDES, 58, 143 SULFIDE SYNTHESIS UNSYMMETRI-CAL DIALKYL DISULFIDES, 58, 147 SULFONYL CYANIDES, 57, 88 Sulfur tetrafluoride, 57, 51... 

Wc-Diols can also be deoxygenated indirectly, through sulfonate ester derivatives. For example, vic-dimesylates and Wc-ditosylates have been converted to alkenes by treatment, respectively, with naphthalene-sodium271 and with Nal in dimethylformamide.272 In another procedure, the diols are converted to bisdithiocarbonates (bis xanthates), which undergo... 

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