Bauhinoxepins A and B: New Antimycobacterial Dibenzo[b,f]oxepins from Bauhinia saccocalyx

Two new antimycobacterial dibenzo[b,f]oxepins, bauhinoxepins A (=3,3,5‐trimethylbenzo[b]pyrano[g][1]benzoxepin‐6,11‐diol; 1 ) and B (=6‐methoxy‐7‐methyl‐2‐(3‐methylbut‐2‐enyl)dibenzo[b,f]oxepine‐1,8‐diol; 2 ), were isolated from the roots of Bauhinia saccocalyx, and their structures were elucidated by analysis of spectroscopic data. Bauhinoxepins A and B exhibited antimycobacterial activities with respective minimum‐inhibitory concentrations (MIC) of 6.25 and 12.5 μg/ml. They were inactive (at 20 μg/ml) against the malarial parasite, and also inactive (at 20 μg/ml) towards the Vero, KB, and BC cell lines.     

Vinylogous dieckmann condensation: an application of Baldwin's rules.

Vinylogous Dieckmann condensations equivalent to enolexo-exo-trig and enolendo-exo-trig cyclisations have been investigated. Five membered rings were smoothly obtained from the former whereas the latter cyclisations occurred with six but not with five membered ring systems.     

Generation and reactions of novel oxiranyl ‘Remote’ anions

Deprotonation of an oxiranyl β-proton takes place in a stereoselective manner providing the corresponding oxiranyl ‘remote’ anion. The anion is stabilized by chelation between the lithium and the carbonyl moiety of an ester, lactone, imide, or keto-group in the form of a five-membered cyclic intermediate. Certain ester-stabilized oxiranyl anions are stable and can be left in THF solution at −78°C for several hours. The generated anions undergo a stereoselective alkylation reaction to provide products, which could be useful intermediates in the synthesis of bioactive naturally occurring α-methylene bis-γ-butyrolactones.     

Isomeric exocyclic and endocyclic dienolates: behavior towards electrophiles

Isomeric exocyclic and endocyclic dienolates 5 and 6 were generated and while 6 reacted with electrophiles exclusively at the α -position the regiospecificity of 5 was found to be dependent on the type of electrophile employed.     

Regiospecific michael additions to α-methylene cyclopentenones

Nucleophiles add in a Michael fashion to α-methylene cyclopentenones regiospecifically at the exocyclic cisoid-enone double bond.     

Stereoselective synthesis of naturally occurring alpha-methylenebis-gamma-butyrolactones: an application of novel oxiranyl "remote" anions.

Stereospecific deprotonation of the epoxy proton at the beta-position of the alpha,beta-epoxy esters 5 and 6 yielded oxiranyl "remote" anions 7 and 8, which could then be used for alkylation. The anions 7 and 8 underwent a consecutive aldol lactonization to give, respectively, epoxy lactones 11 and 13 with high stereoselectivity. Generation of the remote anions as well as their stereoselective reactions served as a new synthetic route to the naturally occurring alpha-methylenebis-gamma-butyrolactones, 1.     

Transformation of an irregularly bridged epidithiodiketopiperazine to trichodermamide A

[reaction: see text] An unusually bridged epidithiodiketopiperazine, pretrichodermamide A (3), was isolated from the fungus Trichoderma sp. BCC 5926. During the extensive effort to crystallize 3 for X-ray crystallographic analysis, conversion of this compound to trichodermamide A with coproduction of S(8) occurred.     

Unusual enniatins produced by the insect pathogenic fungus Verticillium hemipterigenum: isolation and studies on precursor-directed biosynthesis

Two new enniatins H (3) and I (4), whose substituents on 2-hydroxycarboxylic acid moieties were different from those of known compounds, were isolated, together with known enniatins B (1) and B₄ (2), from the insect pathogenic fungus Verticillium hemipterigenum BCC 1449. Structures of these compounds were elucidated by spectroscopic means. Studies on precursor-directed biosynthesis with strain BCC 1449 led to the production and identification of three analogs, enniatins G (5), C (6) and MK1688 (7), as well as the stereochemical elucidation of 3 and 4. Enniatins 1-7 were evaluated for their antiplasmodial and antimycobacterial activities.