Simplified Preparation of 6-Hydroxytropinone.

Norcaradiene intermediates in mass spectral fragmentations of tropone and tropothioneElectronic supplementary information (ESI) available: reaction paths supporting Figs. 3–6. See http://www.rsc.org/suppdata/p2/b1/b102127n/

“…Scheme 2 shows the synthetic route to 2-d 2 via 1-d 2 , which was prepared starting from 2,5-dimethoxy-2,5-dihydrofuran. 14 The obtained 6-hydroxytropinone 15 (3) in the first step was deuteriated repeatedly with D 2 O (isotopic purity: 99.8%) under basic conditions to give 6-hydroxy [2,2,4 The positions of deuteriation in tropone and tropothione have been verified by 1 H and 13 C NMR spectroscopy. We have performed not only one-dimensional 1 H NMR with resolution enhancement 16,17 but also two-dimensional 1 H-1 H shift correlation spectroscopy 18 as a detailed analysis for 1-d 2 and 2-d 2 .…”

Enantioselective oxidation of unactivated C–H bonds in cyclic amines by iterative docking-guided mutagenesis of P450BM3 (CYP102A1)

“…The tropane alkaloid (3S,6S,aS)-anisodamine (6β-hydroxyhyoscyamine) is an anticholinergic and a1 adrenergic receptor antagonist from Anisodus tanguticus. This alkaloid is manufactured as a racemic mixture of diastereomers from (±)-6β-hydroxytropinone [61][62][63] and (±)-tropic acid for the treatment of septic shock and circulatory disorders. 64 To our knowledge, no synthesis of single anisodamine stereoisomers has been reported although relevant enantioenriched intermediates have been prepared in multistep routes by asymmetric synthesis, [65][66][67][68] from (R)or (S)-malic acid, 69 and by resolution.…”

Selective hydrolysis of dihydrocinnamate ester protecting groups by .alpha.-chymotrypsin. Scope and limitation of the method

“…Chem., 207, 443 (1954). were studied using an enzyme concentration of 3.7 X 10 ~6 M. For comparison purposes, the fcos values for both compounds were also determined in the same solvent composition using pll 11 solutions. The data for methyl dihydro cinnamate in 20% acetonitrile were obtained using a substrate concentration range of 1-7 mili and -chymotrypsin at 4.15 X 10 ~7 .…”

“…The C-3 and C-6 configurations assigned14 to the compounds of Scheme II were supported by the chemical shifts and multiplicities observed for the protons at these positions. In the spectra of the 3-oxotropanes 11 and 16 the C-6a protons appeared as triplets. However, when 3a-hydroxy or ester functions were present, the multiplicity of this peak changed to a doublet of doublets.…”

“…Selective13 hydrolysis of the 68-ester function of 13 proceeded smoothly and the 3a-dihydrocinnamate 14 obtained was converted into the mixed diester 15 by treatment with acetic anhydride. Conversion of 68-hydroxytropinone (11) into the 68acetoxy ketone 16 followed by hydrogenation over Raney nickel to the 3a-hydoxy-68-acetate 17 and then treatment with dihydrocinnamoyl chloride provided a convenient alternative synthesis of 15. The C-3 and C-6 configurations assigned14 to the compounds of Scheme II were supported by the chemical shifts and multiplicities observed for the protons at these positions.…”