Synthesis of L-α-Glycerylphosphoryl-L-serine¹

Abstract

PERCENTAGR nF cis ISOMER PRODUCRD 4-Phenylmercaptocamphane (XI).-4-Campliyllithium was prepared following the procedure described by Winstein .' The 4-camphyllithium reagent in cyclohexane was filtered through the sintered glass funnel directly into a solution of cyclohexane containing 10 g. (7.2 g., 0.067 mole required) of phenyl disulfide. As the lithium reagent was added, the reactiou mixture turned milky white, but very little heat was evolved. After the addition was complete, the mixture was heated undcr reflux for 2 to 3 hours. The reaction mixture was then cooled and added slowly t o a solution of 5 g. of lithium aluminum hydride in ethyl ctlicr t o reduce the excess phenyl disulfide t o thiophenol. After the reduction was complete, the excess hydride was destroyed with ethyl acetate, and the solution was poured slowly into excess 6 N sulfuric acid solution containing much chopped ice. After separation of the organic layer, the water layer was extracted twice with cyclohexane. The combined organic layers were then extracted five times with equal volumes of 570 sodium hydroxide solution, washrd with water, and dried over anhydrous potassium carbonate. The solvent was removed at atmospheric pressure through a column, and the residue was heated gently in a subliming tube under reduced pressure (15 mm.). Unreactcd 4-chlorocamphane, 2.75 g. (24% recovery), sublimed onto the walls of the tube and was carefully removed. The yellow residual oil was then distilled under reduced pressure. On redistillation, 10.2 g. (62%) of 4-phenylmercaptocamphane was obtained as a colorlcss oil, which could not be induced t o crystallize, b.p. 110--12l0 (0.1 mm.), n% 1.5567.

Selective Rearrangements of Quadruply Hydrogen‐Bonded Dimer Driven by Donor–Acceptor Interaction

“…Diols 11 b and 11 d were prepared according to the literature from the corresponding dienes 8 b and 8 d by means of the corresponding endo ‐peroxides,46, 47 which were reduced without isolation with activated Zn in CH 2 Cl 2 /acetic acid 48. 49 Diol 11 c and (±)‐ trans ‐cyclohex‐2‐ene‐1,4‐diol were prepared according to the literature from the corresponding dienes 8 c and 8 b through a Pd‐catalyzed 1,4‐diacyloxylation 50. 51 [Pd 2 (dba) 3 ] ⋅ CHCl 3 ,52 bisphosphane 2 ,1 and cycloheptadiene 8 c 53, 54 were prepared according to the literature.…”

Redox Reaction of the Pd0 Complex Bearing the Trost Ligand with meso‐Cycloalkene‐1,4‐biscarbonates Leading to a Diamidato PdII Complex and 1,3‐Cycloalkadienes: Enantioselective Desymmetrization Versus Catalyst Deactivation

“…Diols 11 b and 11 d were prepared according to the literature from the corresponding dienes 8 b and 8 d by means of the corresponding endoperoxides, [46,47] which were reduced without isolation with activated Zn in CH 2 Cl 2 /acetic acid. [48,49] Diol 11 c and (AE )-trans-cyclohex-2-ene-1,4-diol were prepared according to the literature from the corresponding dienes 8 c and 8 b through a Pd-catalyzed 1,4-diacyloxylation. [50,51] [Pd 2 -A C H T U N G T R E N N U N G (dba) 3 ]·CHCl 3 , [52] bisphosphane 2, [1] and cycloheptadiene 8 c [53,54] were prepared according to the literature.…”

Chemical and Enzymatic Approaches to Esters ofsn‐Glycero‐3‐Phosphoric Acid

“…Alternatively, as in the case of GPC (see paragraph 3.1), GPE can be prepared by deacylation of PE contained in lecithin. [81][82][83]104] To date, no enzymatic approaches have been reported for GPE synthesis.…”