Terpenes. II. The Stereochemistry and Absolute Configurations of the Thujylamines and Some Related Compounds¹

(-)-3-Isothujone, a small nonnitrogenous molecule with antinociceptive activity in mice

“…We have confirmed this report and have developed the following preparative method (Scheme I) for racemic 3-isothujone (6) . Low-temperature (-75°) L1AIH4 reduction of the ketone mixture described above proceeded with high stereospecificity, as reported by Banthorpe16 in his product-distribution studies, to give an alcohol mixture from which pure (-)-3-isothujanol (9) was easily isolated through the crystalline (-) -p-nitrobenzoate 14. Reaction of this alcohol with excess p-toluenesulfonyl chloride, although a slow reaction, gave the moderately stable tosylate 10 in high yield. Acetolysis of the tosylate gave the oily acetate 12 along with a minor unidentified side product.…”

“…However, purification of the alcohol has required a tedious fractional distillation,7 12 recrystallizations of a derivative,15 or preparative GLC.16 Goryaev17 has reported that Meerwein-Ponndorff-Verley (MPV) reduction of 2 provided approximately equal amounts of 7 and (+)-3-thujanol (8). However, these results are in disagreement with those of Banthorpe,16 whose nonpreparative, product ratio studies of the reduction of 1 and 2 with several reagents indicated that MPV reduction of 2 gave an 87:13 ratio of (-)-3-neoisothujanol ( 7) to (-)-S-isothujanol (9). Kinetic studies of this reduction by Hach18 have subsequently confirmed the identity of the products reported by Banthorpe and the high ratio of 7 to 9.…”

Zirconium-Catalyzed Oxidation of Primary Aliphatic Amines to Nitro Compounds withtert-Butyl Hydroperoxide

“…The lowest yields (50%, entry 9) are obtained with benzylic amines. The reaction time with sterically hindered substrates such as (Ϫ)-menthylamine (7) [23] increases the reaction time only slightly and the yield of the nitro compound 19 is even increased compared to less sterically hindered amines (94%, entry 7). Equatorial or axial amino groups present in the cis-and trans-4-tert-butylcyclohexylamines 8a and 8b are oxidized to the corresponding nitro compounds 20a and 20b with comparable rates as shown by kinetic experiments.…”

The Synthesis of Nitro and Dimeric Nitroso Sugars by Peracid Oxidation of Amino Sugars

“…Whereas permanganate oxidation is limited to tertiary carbinatnines (2) and therefore is not apt to become a general method for the plirpose stated, peracid oxidation offered itself as a potential alternative. Aliphatic amiiies have been oxidized to the corresponding nitro c o n i p o~~n d s by means of peracetic acid (3,4), perbenzoic acid (5), and n7-chloroperbenzoic acid (6). Trifluoroperacetic acid has been stated (3) to be ~~nsuitable for oxidation of amines although it is capable of converting oximes to nitro compounds (7,8); applications to carbohydrate oximes were reported (9) while the present work was in progress.…”

“…N o nitroso derivative was found in this one case. ' When methyl 3-amino-3,6-dideoxy-a-D-glucopyranoside (4) was oxidized for 1 h with 3 niol equiv of oxidant in refluxing chloroform, the nitroso dimer 5 was isolated in 75% yield as thc sole product, although complete absence of nitro compound 6 was not ascertained. An increased amount of oxidant (4.25 mol equiv) gave rise to a m i x t~~r e of 5 and 6 in which, according to an estimate from the n.m.r.…”