84077-49-6

Upstream product

• 87927-63-7 4α,5α-dimethyl-4β-(2''-1'',3''-dithiolan)-3α-(4'-hydroxybutyl)cyclohexanol 
• 87927-55-7 4β(2'-1',3'-dithiolan)-4α,5α-dimethylcyclohex-2-enone 
• 87927-56-8 3α-but-3'-enyl-4α,5α-dimethyl-4β-(2''-dithiolan)-cyclohexanone 
• 84098-30-6 3-((1S,2R,4S,4aR,8aR)-4-Acetoxy-4a-acetoxymethyl-1,2-dimethyl-5-methylene-decahydro-naphthalen-1-yl)-propionic acid methyl ester 
• 84077-46-3 Acetic acid (1S,3R,4S,4aR,8aR)-8a-acetoxymethyl-4-(4-hydroxy-3-oxo-butyl)-3,4-dimethyl-8-methylene-decahydro-naphthalen-1-yl ester 
• 84077-47-4 Acetic acid (1S,3R,4S,4aR,8aR)-8a-acetoxymethyl-4-[2-(2-hydroxymethyl-[1,3]dioxolan-2-yl)-ethyl]-3,4-dimethyl-8-methylene-decahydro-naphthalen-1-yl ester 
• 87927-58-0 4α,5α-dimethyl-5β-(2-1',3'-dithiolan)-6β-bicyclo<4.4.0>-dec-1(10)-en-2-one 
• 111724-15-3 8β-(2'-1',3'-dithiolan)-8α,9α-dimethyl-1,4-dithiaspiro<4.5>dec-6-ene 
• 80267-24-9 4β-formyl-4α,5α-dimethylcyclohex-2-enone 
• 497-03-0 2-methylbut-2-enal 
• 87927-67-1 (6α,18-dihydroxy)acetonide-12-phenylsulphonylcleroda-4,13(14)-dieno-16,15-lactone 
• 73818-55-0 Bestmann ylide 
• 84077-48-5 1-Hydroxy-4-((1S,2R,4S,4aR,8aR)-4-hydroxy-4a-hydroxymethyl-1,2-dimethyl-5-methylene-decahydro-naphthalen-1-yl)-butan-2-one 
• 83637-77-8 3-((3aR,6aR,7S,8R,10S,10aR)-10-Acetoxy-7,8-dimethyl-decahydro-2-oxa-cyclopenta[d]naphthalen-7-yl)-propionic acid methyl ester 

Downstream Products

• 62640-05-5 ajugarin I 
• 62640-05-5 4-epi-ajugarin I 
• 62640-05-5 ajugarin I 

Relevant academic research and scientific papers

TOTAL SYNTHESIS OF THE INSECT ANTIFEEDANT AJUGARIN I AND DEGRADATION STUDIES OF RELATED CLERODANE DITERPENES

The first total synthesis of the diterpene clerodane insect antifeedant ajugarin I (1) has been achieved.The key step of the synthesis discloses the use of the 1,3-dithiolane unit to stereochemically direct the conjugate addition of a but-3-enyl cuprate to set in place the C-10 sp3 carbon centre.The trans-fused ring geometry was obtained by conjugate addition of a vinyl cuprate to an enone and regio and stereoselectively trapping the resulting enolate with formaldehyde.Introduction of the necessary butenolide side chain was achieved by conjugate addition of a sulphone stabilised anion to ethyl-4-(t-butyldimethylsilyloxy)but-2-ynoate followed by work-up with fluoride.Final hydroxyl directed epoxidation was not specific giving both the natural product ajugarin I and its 4-epi isomer.Chemical modification of the insect antifeedant clerodin hemiacetal afforded a series of side chain modified structures for biological evaluation.

INVESTIGATIONS INTO THE TOTAL SYNTHESIS OF INSECT ANTIFEEDANT CLERODANES THE TOTAL SYNTHESIS OF +/- 4-EPI AJUGARIN

Starting from alcohol 3, a stereospecific synthesis of carboxylic acid 2 is described.This acid 2 is a key intermediate in the total synthesis of ajugarins and its conversion into +/- 4-epi ajugarin is reported.