Synthesis of (+)- and (-)-N-BOC-7-Azabicyclo[2.2.1]heptan-2-ones, Versatile Intermediates for the Enantiospecific Synthesis of (+)- and (-)-Epibatidine and Analogs

Abstract

Synthesis of (+)-and (-)-iV-BOC-7-Azabicyclo[2.2.1]heptan-2-ones, Versatile Intermediates for the Enantiospecific Synthesis of (+)and (-)-Epibatidine and Analogues

Synthesis of 1,2‐Dioxane Type Antimalarial Peroxides†

“…The mild I 2 /NaHCO 3 condition led to no reaction at all. H 5 IO 6 14 gave better results, giving 42 in 14% yield. NBS 15 appeared to afford slightly improved yield (25%), but which was still not satisfactory.…”

Bicyclic β-amino acids

“…139 In particular, carboxylic acid 300 was protected at both functions and then subjected to α-hydroxylation to give alcohol 302. Reaction of 302 with with Tf 2 O and then -thioamide 301, M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT followed by heating of the adduct in N-methylpyrrolidone (NMP) led to the formation of olefine 303, which was hydrogenated and then hydrolyzed to give the product 304 as a mixture of diastereomers.…”

Toward an Asymmetric General Access to Azabicyclo[n.2.1]alkanes According to the CN(R,S) Method

“…IR ( 1.41 (s, 9 H), 1.40 (s, 9 H). 13 C NMR (62.5 MHz, CDCl 3 ): δ (two rotamers) ϭ 18.0, 18. 3,24.5,25.3,27.3,27.9,28.2,28.4,28.6,29.1,29.7,51.9,53.0,53.7,54.2,54.7,79.4,152.9,153.3,208.9,209.2.…”

“…C 18 13 C NMR (62.5 MHz, CDCl 3 ): δ ϭ 28. 9, 29.1, 33.4, 37.3, 63.8, 64.7, 65.8, 75.5, 98.3, 103.4, 120.9, 126.2, 127.3, 128.7, 141.9.…”

“…For similar work in this field, Rapoport reported better results by applying the intramolecular Mannich-type cyclisation onto a more electrophilic acyliminium ion. [13] Using the same strategy as above, the 8-azabicyclo[3.2.1] skeleton 12b was successfully isolated in 66% yield. This transformation was totally stereoselective: only one stereoisomer was present in the crude mixture as indicated by 1 H and 13 C NMR spectrosopcy.…”