The π-route to 2,4-substituted adamantanes

Reduction of Adamantanone: Face Selection Induced by 4-Halo and 4,9-Dihalo Substitution

“…The reductions were done with sodium borohydride in methanol at 0 °C (Table ). The product ratios were determined by means of 1 H NMR; the published 1 H and 13 C NMR spectra are in agreement with ours for both the ketones 1 − 2 -F and -Br ,, and alcohols 4 − 7 -F and -Br. ,,− The assignments of ( E )- and ( Z )- 13 were made by means of the unseparated mixture; the addition of Eu(fod) 3 clearly resulted in a downfield shift of the CHBr protons in the latter compound much larger than those in the E -isomer.…”

“…Thus, McKervey reported that the sodium borohydride reduction of 1 -Br gives exclusively 4 -Brsurely a consequence of the size of the bromine atom. The same group also reported that the reduction of 1 -OH with lithium aluminum hydride yields coaxial 4 -OH in a 19:1 excess over isomer 5 -OH; both H-bonding and the size of the 4-hydroxy group may have contributed to this result. More pertinent to our present purpose is the fact that the same reduction of adamantane-2,4-dione ( 3 ) gave 4 -OH, 5 -OH, and 7 -OH in a ratio of 45:39:16, respectively (note that 5 - and 6 -X are identical when X is OH).…”

Reactions of 2-anti-hydroxy-4-aza-5-homoadamantan-5-one

“…All compounds were purified by column chromatography on silica gel with various ligroin/acetone mixtures as eluants and were >98% pure. Compounds already known in literature (5,2 7,1,4,5 9,5 with their published spectra. Except for 5, authentic samples were available for comparison by thin-layer chromatography and by their NMR spectra.…”

Deuterium and the octant rule for ketones. Syntheses and circular dichroism data of chiral 4-deuterioadamantan-2-ones

“…4-Deuterioadamantan-2-ol (17) (0.08 g) was treated with Jones reagent as described above for the (lS)-4(e)-deuterioadamantan-2-one (5). Purification by HPLC and sublimation afforded the 4(a)-deuterioadamantan-2-one (18) (same conditions as for 5): yield 0.05 g (63%); mp 250-253 °C; [a]546 +1.2 ± 0.4°(c 0.48, isooctane); IR (KBr disk) 1725 (C=0), 2100, 2180 cm"1 (CD); NMR (CDClg) 2.65-2.45 (2 ), 2.30-1.70 (3JR)-3-Hydroxydideuteriomethylbicyclo[3.3.1]non-6-ene (9). A solution of endo-bicyclo[3.3.1]non-6-en-3-carboxylic acid (1) (1.9 g, [«[573 +126.4°, c 0.5, 96% ethanol) in ether (100 mL) was added dropwise to a stirred slurry of lithium aluminum deuteride (3.8 g) in ether (20 mL).…”

“…(1 S)-4,4-Dideuterioadamantan-2-ol (20). 9 (1.28 g) was added to a stirred solution of p-toluenesulfonyl chloride (1.58 g) in dry pyridine (100 mL) at 0 °C. The mixture was kept at 8 °C for 48 h and then was poured into cold water and extracted with ether (3 X 50 mL).…”