28357-11-1

Upstream product

• 10334-26-6 (R)-camphorquinone 
• 279673-36-8 C₂₇H₃₈N₂O₆ 
• 279673-28-8 methyl (2S,2'R,3S,3'S,3aS,4aS,5R,8S,8aR)-3-(2,5,10,10-tetramethyl-octahydro-2H-5,8-methano-isoxazolo[3,2-b]benzoxazol-3-yl)-3'-(phenylmethyloxycarbonyl)amino-2'-methylpropanoate 
• 862425-08-9 (1S,2R,5S,8R,1'S)-5-(1'-hydroxy-iso-butyl)-8,11,11-trimethyl-3-oxa-6-azatricyclo[6.2.1.0(2,7)]undec-6-en-4-one 
• 862425-09-0 (1S,2R,5S,8R,1'S)-5-(1'-hydroxy-1'-cyclohexylmethyl)-8,11,11-trimethyl-3-oxa-6-azatricyclo[6.2.1.0(2,7)]undec-6-en-4-one 
• 1111092-08-0 (1S,2R,5S,8R,1'R)-5-(1'-hydroxybenzyl)-8,11,11-trimethyl-3-oxa-6-azatricyclo[6.2.1.0(2,7)]undec-6-en-4-one 
• 1111092-11-5 (1S,2R,5S,8R,1'R)-5-(1'-hydroxy-o-fluorobenzyl)-8,11,11-trimethyl-3-oxa-6-azatricyclo[6.2.1.0(2,7)]undec-6-en-4-one 
• 1111092-12-6 (1S,2R,5S,8R,1'R)-5-(1'-hydroxy-o-chlorobenzyl)-8,11,11-trimethyl-3-oxa-6-azatricyclo[6.2.1.0(2,7)]undec-6-en-4-one 
• 464-49-3 (1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one 
• 464-48-2 (1S)-camphor 
• 15795-31-0 Acetic acid (1S,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]hept-2-yl ester 
• 10293-06-8 (1R)-3-endo-bromocamphor 

Downstream Products

• 123820-99-5 (1R,3R,exo)-N-benzyl-2-imino-3-hydroxy-1,7,7-trimethylbicyclo<2.2.1>heptane 
• 123821-00-1 (1R,2S,3R,exo)-N-benzyl-2-amino-3-hydroxy-1,7,7-trimethylbicyclo<2.2.1>heptane 
• 159849-35-1 (1S,2R,6S,7R,exo)-N-cinnamoyl-3-oxa-5-aza-7,10,10-trimethyltricyclo<5.2.1.0^2,6>decan-4-one 
• 174901-73-6 3-exo-(2-methoxyethoxy)-2-exo-bornyl phenylethanoate 
• 123821-09-0 (1S,2R,6S,7R)-7,10,10-Trimethyl-4-((1S,6S)-3,4,6-trimethyl-cyclohex-3-enyl)-3-oxa-5-aza-tricyclo[5.2.1.0^2,6]dec-4-ene 
• 123821-02-3 (Z)-N-((1R,2S,3R,4S)-3-Hydroxy-1,7,7-trimethyl-bicyclo[2.2.1]hept-2-yl)-3-phenylsulfanyl-acrylamide 
• 129064-39-7 (1S,2R,6S,7R)-7,10,10-Trimethyl-4-((1S,2S,6S)-6-methyl-2-phenylsulfanyl-cyclohex-3-enyl)-3-oxa-5-aza-tricyclo[5.2.1.0^2,6]dec-4-ene 
• 123924-27-6 (1S,2R,6S,7R)-7,10,10-Trimethyl-4-((Z)-2-phenylsulfanyl-vinyl)-3-oxa-5-aza-tricyclo[5.2.1.0^2,6]dec-4-ene 
• 123821-04-5 (1S,2R,6S,7R)-4-((Z)-2-Benzenesulfonyl-vinyl)-7,10,10-trimethyl-3-oxa-5-aza-tricyclo[5.2.1.0^2,6]dec-4-ene 
• 123821-08-9 (1S,2R,6S,7R)-4-((1S,2R,3R,4R)-3-Benzenesulfonyl-bicyclo[2.2.1]hept-5-en-2-yl)-7,10,10-trimethyl-3-oxa-5-aza-tricyclo[5.2.1.0^2,6]dec-4-ene 
• 123821-08-9 (1S,2R,6S,7R)-4-((1R,2R,3R,4S)-3-Benzenesulfonyl-bicyclo[2.2.1]hept-5-en-2-yl)-7,10,10-trimethyl-3-oxa-5-aza-tricyclo[5.2.1.0^2,6]dec-4-ene 
• 10334-26-6 (R)-camphorquinone 
• 28357-12-2 2-exo-3-endo camphane-2,3-diol 
• 68738-11-4 (+)-2-endo-3-exo-camphane-2,3-diol 

Relevant academic research and scientific papers

Exploring the substrate specificity of Cytochrome P450cin

Cytochromes P450 are enzymes that catalyse the oxidation of a wide variety of compounds that range from small volatile compounds, such as monoterpenes to larger compounds like steroids. These enzymes can be modified to selectively oxidise substrates of interest, thereby making them attractive for applications in the biotechnology industry. In this study, we screened a small library of terpenes and terpenoid compounds against P450cin and two P450cin mutants, N242A and N242T, that have previously been shown to affect selectivity. Initial screening indicated that P450cin could catalyse the oxidation of most of the monoterpenes tested; however, sesquiterpenes were not substrates for this enzyme or the N242A mutant. Additionally, both P450cin mutants were found to be able to oxidise other bicyclic monoterpenes. For example, the oxidation of (R)- and (S)-camphor by N242T favoured the production of 5-endo-hydroxycamphor (65–77% of the total products, dependent on the enantiomer), which was similar to that previously observed for (R)-camphor with N242A (73%). Selectivity was also observed for both (R)- and (S)-limonene where N242A predominantly produced the cis-limonene 1,2-epoxide (80% of the products following (R)-limonene oxidation) as compared to P450cin (23% of the total products with (R)-limonene). Of the three enzymes screened, only P450cin was observed to catalyse the oxidation of the aromatic terpene p-cymene. All six possible hydroxylation products were generated from an in vivo expression system catalysing the oxidation of p-cymene and were assigned based on 1H NMR and GC-MS fragmentation patterns. Overall, these results have provided the foundation for pursuing new P450cin mutants that can selectively oxidise various monoterpenes for biocatalytic applications.

In vivo and in vitro hydroxylation of cineole and camphor by cytochromes P450CYP101A1, CYP101B1 and N242A CYP176A1

Cytochromes P450 (P450s) are valuable enzymes that can generate a range of useful compounds via biocatalytic oxidations that complement traditional synthetic chemistry. In this study three bacterial P450s, P450cam (CYP101A1), CYP101B1 and the m

General and efficient α-oxygenation of carbonyl compounds by TEMPO induced by single-electron-transfer oxidation of their enolates

A generally applicable method for the synthesis of protected α-oxygenated carbonyl compounds is reported. It is based on the single-electron-transfer oxidation of easily generated enolates to the corresponding α-carbonyl radicals. Coupling with the stable free radical TEMPO provides α-(piperidinyloxy) ketones, esters, amides, acids or nitriles in moderate-to-excellent yields. Enolate aggregates influence the outcome of the oxygenation reactions significantly. Competitive reactions have been analyzed and conditions for their minimization are presented. Chemoselective reduction of the products led to either N-O bond cleavage to α-hydroxy carbonyl compounds or reduction of the carbonyl functionality tomonoprotected 1,2-diols or O-protected amino alcohols. The oxygenation of enolates proves to be the most general and effective methodology for the synthesis of O-protected α-oxy carbonyl compounds and nitriles A. The scope and limitations of the electron-transfer-induced radical coupling reaction with TEMPO are presented. The reaction pathways are outlined. Methods for the deprotection to α-hydroxy carbonyl compounds B are provided and discussed. Copyright

Diastereo- And enantioselective synthesis of β-Hydroxy-α-amino acids: Application to the synthesis of a key intermediate for lactacystin

The development of a highly efficient and stereoselective methodology for the preparation of β-hydroxy-α- amino acids is described. Nucleophilic addition of enolates of tricyclic iminolactones 1a and 1b to aldehydes in the presence of 6 equiv of lithium chloride in THF at -78 °C leads to aldol adducts in good yield (63-86%) and high diastereoselectivity (up to >25:1 dr). Subsequently, hydrolysis of the aldol adducts under acidic conditions leads to the corresponding β-hydroxy-a-amino acids in good yields (up to 83%) and excellent enantiomeric excesses (99% ee) with good recovery yields of the chiral auxiliaries 6 and 7. This methodology was applied to the facile synthesis of the key intermediate for lactacystin along with several isomers.

Reduction of various ketones by red algae

The reduction of acetophenone derivatives, (+)- and (-)-camphorquinones and steroidal ketones using red algae (Cyanidioschyzon merolae 10D and Cyanidium caldarium) was investigated. It was found that fluoro, chloro and bromo acetophenone derivatives 1a-i were reduced with good enantioselectivity. On the contrary, reduction of methyl and methoxy acetophenone 1j-o showed low enantioselectivity. The reduction followed Prelog's rule, giving the (S)-alcohols in all cases. Moreover, (+)- camphorquinone 5a was reduced to give (-)-3S- exo-hydroxycamphor 5d as the major product with high stereoselectivity in high yield. In addition, it was found that reduction of 5α-androstane-3,17-dione 8a gave the 3α-OH isomer (3α-OH/3β-OH = 76/24) with high stereoselectivity. Overall it was found that C. merolae and C. caldarium were able to reduce various substrates.

A novel synthesis of α-hydroxy- and α,α′- dihydroxyketone from α-iodo and α,α′-diiodo ketone using photoirradiation

A novel reaction of α-iodo ketone (α-iodocycloalkanone, α-iodo-β-alkoxy ester, and α-iodoacyclicketone) with irradiation under a high-pressure mercury lamp gave the corresponding α-hydroxyketone in good yields. In the case of α,α′- diiodo ketone, α,α′-dihydroxyketone which little has been reported until now was obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxy- and α,α′- dihydroxyketone.

Biotransformation of (+)- and (-)-camphorquinones by plant cultured cells

Biotransformation of (+)- and (-)-camphorquinones with suspension plant cultured cells of Nicotiana tabacum and Catharanthus roseus was investigated. It was found that the plant cultured cells of N. tabacum and C. roseus reduce stereoselectively the carbonyl group of (+)- and (-)-camphorquinones to the corresponding α-keto alcohols.

Oxazoline N-oxide mediated [3+2] cycloadditions: Application to a formal synthesis of a (+)-β-methylcarbapenem

[3+2] Cycloaddition between a camphor-derived oxazoline N-oxide 9 and the γ,δ-unsaturated enamino ester 11 afforded the single adduct 6. A stereoselective reduction of the enamino ester side chain allowed the control of the absolute configuration of the two additional asymmetric centres. Nitrogen protection and oxidative hydrolysis of the resulting product 13, followed by further functional group manipulations, led to the β-lactam derivative 1, a known precursor of the β-methylthienamycin derivative 2a.

Camphor-Derived Alcohols: An Anomalous Reaction of 3-Hydroxycamphor and the Influence of Internal Alkoxides on the Alkylation Stereochemistry of Glycinate Imines

Attempted imine formation between 3-hydroxycamphor and tert. butyl glycinate led to 8, the substitution product at the 3-position.Zinc-acetic acid treatment of 8 afforded 3-acetoxycamphor.Alkylation of the imine from norcamphor and tert. butyl glycinate gave no stereoselection.Alkylation of the imine from 10-hydroxymethylcamphor and tert. butyl glycinate gave stereoselectivities inferior to those obtained from the imine of camphor itself (1), but aldol condensation with benzaldehyde, a reaction not possible with 1, was effected in 71percent yield.