127604-97-1

Upstream product

• 128684-89-9 (1R,3R,4R) methyl 4-hydroxy-3-methoxy-1-cyclohexanecarboxylate 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 133407-52-0 (1R,4R,5R)-4-benzoyloxy-6-oxabicyclo[3.2.1]octan-7-one 
• 133407-50-8 3,4-O-benzylidene-1,5-quinolactone 
• 133407-51-9 (1S,3S,4S,5R)-4-benzoyloxy-3-bromo-6-oxabicyclo[3.2.1]octan-7-one 
• 158981-05-6 methyl (1R,3R,4R)-4-benzoyloxy-3-hydroxycyclohexane-1-carboxylate 
• 133429-54-6 methyl (1R,3R,4R)-4-benzoyloxy-3-methoxycyclohexane-1-carboxylate 
• 216662-59-8 3,4-O-benzylidene-1,5-quinolactone 1-O-(S-methylxanthate) 
• 216662-57-6 (1S,3R,4R,5R)-3,4-O-Benzylidene-1,3,4-trihydroxy-6-oxabicyclo<3.2.1>octan-7-one 
• 127604-94-8 3-Cyclohexene-1-carboxylic acid (S)-pantolactone ester 
• 127604-95-9 (1R,5R)-4-(tert-Butyl-dimethyl-silanyloxy)-6-oxa-bicyclo[3.2.1]octan-7-one 
• 116498-92-1 (1R,4R,5R)-4-hydroxy-6-oxabicyclo[3.2.1]octan-7-one 
• 5709-98-8 (R)-cyclohex-3-enecarboxylic acid 
• 127604-96-0 (1R,3R,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-3-hydroxy-cyclohexanecarboxylic acid methyl ester 

Downstream Products

• 128209-98-3 (E)-3-[(1R,3R,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-2-methyl-propenal 
• 127605-03-2 (E)-(2S,3S)-5-[(1R,3R,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-3-methoxymethoxy-2,4-dimethyl-pent-4-enal 
• 127605-01-0 (E)-(2S,3S)-5-[(1R,3R,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-3-hydroxy-2,4-dimethyl-pent-4-enethioic acid S-phenyl ester 
• 127623-75-0 Acetic acid (E)-(3S,4R,5S)-7-[(1R,3R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-3-hydroxy-5-methoxymethoxy-4,6-dimethyl-1-methylene-hept-6-enyl ester 
• 127605-02-1 (E)-(2S,3S)-5-[(1R,3R,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-3-methoxymethoxy-2,4-dimethyl-pent-4-enethioic acid S-phenyl ester 
• 127605-06-5 (E)-(4S,5S,6S)-1-Bromo-4-(tert-butyl-dimethyl-silanyloxy)-8-[(1R,3R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-6-methoxymethoxy-5,7-dimethyl-oct-7-en-2-one 
• 127605-05-4 Acetic acid (E)-(3S,4S,5S)-3-(tert-butyl-dimethyl-silanyloxy)-7-[(1R,3R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-5-methoxymethoxy-4,6-dimethyl-1-methylene-hept-6-enyl ester 
• 127605-08-7 (1E,8E,10E)-(3S,4S,5S)-5-(tert-Butyl-dimethyl-silanyloxy)-1-[(1R,3R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-3-methoxymethoxy-2,4,10,12-tetramethyl-trideca-1,8,10-trien-7-one 
• 127605-07-6 (E)-(4S,5S,6S)-4-(tert-Butyl-dimethyl-silanyloxy)-8-[(1R,3R,4R)-4-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-cyclohexyl]-1-(dimethyl-phenyl-λ⁵-phosphanylidene)-6-methoxymethoxy-5,7-dimethyl-oct-7-en-2-one 
• 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 
• 128209-97-2 (1R,3R,4R)-4-[(tert-butyldimethylsilyl)oxy]-3-methoxycyclohexane-1-carbaldehyde 

Relevant academic research and scientific papers

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.

ENANTIOSELECTIVE SYNTHESIS OF THE C(18)-C(35) SEGMENT OF IMMUNOSUPPRESSANT FK-506 USING EFFICIENT NEW METHODOLOGY

A simple, enantiocontrolled and efficient route to an intermediate containing carbons 18 to 35 of the macrocyclic immunosuppressant FK-506 (1) is described which depends on a sequence of three enantioselective C-C bond forming reactions.