38397-34-1

Upstream product

• 497-38-1 Norbornan-2-on 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 66057-08-7 ((1R,4S)-3-Chloro-bicyclo[2.2.1]hept-2-en-2-yloxy)-trimethyl-silane 
• 33073-39-1 (1R,4R)-2-Hydroxy-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid 
• 16346-63-7 (1R,4R)-(+)-norbornenone 
• 58001-99-3 5-norbornene-2-carboxylic acid 
• 497-38-1 (1S,4R)-bicyclo[2.2.1]heptan-2-one 
• 125093-74-5 (1R,4S)-2-Trimethylsilanyl-3-trimethylsilanyloxy-bicyclo[2.2.1]hept-2-ene 

Downstream Products

• 497-37-0 exo-2-norbornanol 
• 497-36-9 (+/-)-endo-2-norborneol 

Relevant academic research and scientific papers

The 2-norbornyl cation via the fragmentations of exo- and endo-2-norbornyloxychlorocarbenes: Distinction without much difference

exo- and endo-2-norbornyloxychlorocarbenes (7) were generated photochemically from the corresponding diazirines (6). Both carbenes fragmented to [2-norbornyl cation (carbon monoxide) chloride] ion pairs in MeCN or 1,2-dichloroethane solutions. Products included exo-norbornyl chloride (8), endo-norbornyl chloride (9), norbornene (10), and nortricyclene (11). Fragmentation activation energies were very low (5 s-1 in MeCN). Due to chloride return within the ion pairs, product distributions from exo- and endo-7 differed, with more endo-chloride formed from the endo-carbene: the 8/9 product ratio in MeCN was ～41 from exo-7, but only 4.6 from endo-7. Norbornene, formed by proton transfer to Cl- within the ion pairs, was a major product in both cases (44% from exo-7 and 62% from endo-7). In MeOH/MeCN, up to 28% of exo-2-norbornyl methyl ether formed at the expense of some of the norbornene, but even in 100% MeOH, the norbornyl chloride products of ion pair return still accounted for 46% and 31% of the exo-7 and endo-7 product mixtures (accompanied by 26-32% of norbornene). Electronic structure calculations on the ground states and fragmentation transition states of exo-7 and endo-7 are presented.

Stereoselective Introduction of Hydroxyl Groups via Hydrazones

Reduction of tosylhydrazones by hydride reagents in wet alcohol gave predominantly alcohols whose stereochemistries are opposite to those of the major reduction products of the corresponding ketones with sodium borohydride.

β-SILYL CARBENES

β-Trimethylsilyl carbenes rearrange to form alkenes by facile migration of the β-silyl group.In the norbornyl system, β-hydrogen migration can also compete with silyl migration.