Bornyl amine

Highly enantioselective Norrish/Yang photocyclization of di-4-tert-butyl-1-benzoylcyclohexane 47 was also achieved in salt crystals using chiral amines like R)- + )-l-phenylethylamine or (- )-norephedrine [61,63], Furthermore, cis-9-decalyl aryl ketones 49 in their salt crystals with chiral amines such as (/ )-(-I- )-bornyl amine or (S -( — )-l-phenylethylamine underwent highly regio-, dia-stereo- and enantioselective Norrish/Yang photocyclizations to give the cyclobutanol 50 alone in > 98% ee [64],... 

Further experimental evidence to support this equilibrium and the structures of the conformers was obtained from the study of the low-temperature H NMR spectra of the MTPA amides of (-l-)-bornyl-amine. The results (Figure 104a) are consistent with the previously discussed predictions and illustrate the effect of the phenyl ring on the substrate in each conformer. 

Similarly solvolysis of bornyl derivatives and deamination of bornyl amine produce tricyclene is low yield 98,185,186). As in the deamination of isobutylamine, the yield of 1,3-hydrogen elimination increases when the carbonium ion is generated in a non-polar solvent (diglyme), in this case from the tosylhydrazone 187). That the formation of tricyclene... 

Koizumi and co-workers used the optically active allylic chloroselenuranes bearing the 2-exo-hydroxyl-10-bornyl group to obtain optically active allylic amines [41]. The treatment of allylic selenides with f-BuOCl gave the corresponding allylic chloroselenuranes as the only product. Benzyl carbamate, t-butyl carbamate, p-tosylamide, and diphenylphosphinamide were selected as the AT-protected amines for selenimide formation. The nucleophilic reaction of... 

A -Substituted bornyl- and isobornylamines 17-19 are best obtained by reduction of the imines formed from camphor and a suitable amine4, either by isolation of the imine or in situ formation. The substituted amines were used as the lithium salt for enantioselective deprotonation and elimination reactions (Section C ). In almost all cases, the exo-amines (isobornylamines) are formed however, using (S)-l-phenylethylamine as the starting amine, the selectivity is reversed and the enob-amine (bornylamine) is obtained. 

The formation of a-terpineol as the major product from deamination of fenchyl amine (43-NH2) (98) is remarkable in that it requires first rearrangement to the more strained pinane skeleton. Small amounts (3—11%) of pinane-type products have been isolated from the bornyl and fenchyl diazonium ions under alkaline conditions (98 a). The contra-thermodynamic rearrangement of apobornyl and camphenilyl derivatives to nopinone may be effected in good yield with the driving force of the pinacol-type rearrangement (98 b, 99). 

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