133407-51-9

Upstream product

• 133407-50-8 3,4-O-benzylidene-1,5-quinolactone 
• 216662-57-6 (1S,3R,4R,5R)-3,4-O-Benzylidene-1,3,4-trihydroxy-6-oxabicyclo<3.2.1>octan-7-one 
• 216662-59-8 3,4-O-benzylidene-1,5-quinolactone 1-O-(S-methylxanthate) 

Downstream Products

• 155386-27-9 (1R,2R,4R)-1-[(tert-butyldimethylsilyl)oxy]-4-(2,2-dibromovinyl)-2-methoxycyclohexane 
• 155386-28-0 (1R,2R,4R)-1-[(tert-butyldimethylsilyl)oxy]-4-ethynyl-2-methoxycyclohexane 
• 155386-29-1 (1R,2R,4R)-1-[(tert-butyldimethylsilyl)oxy]-2-methoxy-4-(1-propynyl)cyclohexane 
• 128684-89-9 (1R,3R,4R) methyl 4-hydroxy-3-methoxy-1-cyclohexanecarboxylate 
• 128209-97-2 (1R,3R,4R)-4-[(tert-butyldimethylsilyl)oxy]-3-methoxycyclohexane-1-carbaldehyde 
• 127604-97-1 methyl (1R,3R,4R)-4-[(tert-butyldimethylsilyl)oxy]-3-methoxycyclohexane-1-carboxylate 
• 133407-53-1 Toluene-4-sulfonic acid (1R,3R,4R)-3-methoxy-4-triisopropylsilanyloxy-cyclohexylmethyl ester 
• 133429-54-6 methyl (1R,3R,4R)-4-benzoyloxy-3-methoxycyclohexane-1-carboxylate 
• 158981-05-6 methyl (1R,3R,4R)-4-benzoyloxy-3-hydroxycyclohexane-1-carboxylate 
• 133407-54-2 ((1R,2R,4R)-4-Bromomethyl-2-methoxy-cyclohexyloxy)-triisopropyl-silane 
• 109466-73-1 (-)-(1R,2R,4R)-4-hydroxymethyl-2-methoxycyclohexan-1-ol 
• 133407-52-0 (1R,4R,5R)-4-benzoyloxy-6-oxabicyclo[3.2.1]octan-7-one 

Relevant academic research and scientific papers

Studies directed towards the synthesis of immunosuppressive agent FK-506: Synthesis of the entire top-half

An efficient approach has been developed to construct the entire TOP-HALF of FK-506 involving Grignard reaction of a C-29 bromide with a C-27 methylketo fragment.

A practical synthesis of the cyclohexyl part of the immunosuppressant FK506

Starting from the benzylidene lactone 3 of D-(-)-quinic acid the cyclohexyl fragment 15 (C-28-C-34 part) of the immunosuppressant FK506 was synthesized. Key steps include homolytic deoxygenation reactions on compounds 4 and 6 as well as a regioselective opening of the benzylidene acetal 5. Opening of the lactone 7 to provide the methyl ester 8 was followed by methylation of the hydroxy group to give 9. Further steps provided the aldehyde 12 which was elongated to the alkyne 15. This sequence provides 15 in gram quantities.