113457-90-2

Upstream product

• 113457-90-2 (3S,5S,6R,9R,R_S)-3-benzyloxymethyl-9-hydroxymethyl-5-(p-tolyl)sulfinyl-1,7-dioxaspiro<5.5>undecane 
• 100-39-0 benzyl bromide 
• 113457-88-8 (S)-3-Benzyloxymethyl-6-[4-(tert-butyl-diphenyl-silanyloxy)-3-(tert-butyl-diphenyl-silanyloxymethyl)-butyl]-5-(toluene-4-sulfinyl)-3,4-dihydro-2H-pyran 
• 113476-99-6 (R_S)-1,1-bis(tert-butyldiphenylsilyloxymethyl)-7,7-bis(hydroxymethyl)-5-(p-tolyl)sulfinyl-4-heptanone 
• 113477-00-2 1-[4-(tert-Butyl-diphenyl-silanyloxy)-3-(tert-butyl-diphenyl-silanyloxymethyl)-butyl]-7-((S)-toluene-4-sulfinyl)-2,6-dioxa-bicyclo[2.2.2]octane 
• 113493-28-0 (R_S)-5,5-bis(tert-butyldiphenylsilyloxymethyl)-1-(p-tolyl)sulfinyl-2-pentanone 
• 113684-63-2 6-(tert-Butyl-diphenyl-silanyloxy)-5-(tert-butyl-diphenyl-silanyloxymethyl)-1-(toluene-4-sulfinyl)-hexan-2-ol 
• 113476-98-5 4,4-bis(tert-butyldiphenylsilyloxymethyl)butanal 
• 113457-95-7 4,4-bis(hydroxymethyl)butanal ethylene acetal 
• 1519-39-7 (R)-methyl p-tolyl sulfoxide 
• 19515-61-8 diethyl 2-(3-oxo-propyl)malonate 
• 113457-89-9 (3S,R_S)-3-benzyloxymethyl-6-<3,3-bis(hydroxymethyl)propyl>-3,4-dihydro-3-hydroxymethyl-5-(p-tolyl)sulfinyl-2H-pyran 

Downstream Products

• 83780-27-2 (-)-Talaromycin B 
• 113457-93-5 (3S,6R,9R)-3-benzyloxymethyl-9-ethyl-1,7-dioxaspiro<5.5>undec-4-ene 
• 113457-90-2 [(3S,6R,9S,11S)-9-Benzyloxymethyl-11-((R)-toluene-4-sulfinyl)-1,7-dioxa-spiro[5.5]undec-3-yl]-methanol 
• 113457-92-4 (3S,6R,9S)-3-benzyloxymethyl-9-(p-tosyl)oxymethyl-1,7-dioxaspiro<5.5>undec-4-ene 
• 113457-93-5 (3S,6R,9S)-3-benzyloxymethyl-9-ethyl-1,7-dioxaspiro<5.5>undec-4-ene 
• 113457-93-5 (3S,6S,9S)-3-benzyloxymethyl-9-ethyl-1,7-dioxaspiro<5.5>undec-4-ene 
• 113457-94-6 Trifluoro-acetic acid (3S,4S,6R,9S)-3-benzyloxymethyl-9-ethyl-1,7-dioxa-spiro[5.5]undec-4-yl ester 
• 113457-94-6 Trifluoro-acetic acid (3S,4R,6S,9S)-3-benzyloxymethyl-9-ethyl-1,7-dioxa-spiro[5.5]undec-4-yl ester 

Relevant academic research and scientific papers

Synthetic studies on spiroketal natural products. IV. A stereoselective synthesis of (3S,5S,6R,9R,R(S))-3-benzyloxymethyl-9-hydroxymethyl-5-(p-tolyl)sulfin yl-1,7-dioxaspiro[5.5]undecane, a key intermediate for talaromycins

A dioxaspiro compound (4), a common intermediate for the synthesis of talaromycin A (1) and (-)-talaromycin B (2), was synthesized by two routes utilizing two kinds of asymmetric recognition of prochiral 1,3-diols controlled by sulfinyl chirality, that is, firstly by acid promoted diastereoselective C-O bond fission of the bicyclic acetal (7) to give the dihydropyran derivative (6), which has an S-hydroxymethyl group at the C3-position (7 → 6), and secondly by diastereoselective intramolecular Michael addition of the diol (5), in which the three chiral centers at C5, C6, C9 were constructed in one step (5 → 4).

Synthetic studies on spiroketal natural products. V. Total synthesis of (+)-talaromycin A and (-)-talaromycin B

The total synthesis of (+)-talaromycin A and (-)-talaromycin B was accomplished by utilizing a common intermediate (3). The spiroketal (3) was converted to the olefin (4) via thermolysis of the sulfinyl group, C1-unit elongation at the C9-position, and isomerization at the spiro center. On the other hand, 3 was isomerized to 7 at the C9-position and then converted to the olefin (5) in a similar manner to that described for (+)-talaromycin A. These intermediates (4 and 5) were transformed into (+)-talaromycin A and (-)-talaromycin B via addition reaction of trifluoroacetic acid and oxymercuration, respectively.

ASYMMETRIC INDUCTION BY SULFINYL CHIRALITY. A TOTAL SYNTHESIS OF (+)-TALAROMYCIN A AND (-)-TALAROMYCIN B

A total synthesis of (+)-talaromycin A and (-)-talaromycin B was accomplished by means of successive asymmetric induction of all chiral centers using a chiral sulfinyl group.