185030-59-5

Upstream product

• 148516-13-6 (S)-1-chloro-2-hydroxy-5-trimethylsilyl-4-pentyne 
• 460348-12-3 (R)-5-(trimethylsilyl)pent-4-yn-2-ol 
• 929117-83-9 (S,Z)-3-bromo-1-(2-tert-butyldiphenylsilyloxy)ethyl-2-propenyl acetate 
• 1053723-00-4 C₂₆H₃₉O₄Si₂Br 
• 929117-82-8 C₂₆H₃₈O₄Si₂ 
• 851278-46-1 (1R,2R,3R)-5-(tert-butyldiphenylsilyloxy)-1,2-epoxy-1-trimethylsilylpentan-3-ol 
• 929117-84-0 Acetic acid (1S,3R)-1-((E)-2-{(4S,5S)-5-[2-(tert-butyl-diphenyl-silanyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-vinyl)-3-(4-methoxy-benzyloxy)-butyl ester 
• 929117-81-7 (3S,4S,5E,7S,9R)-1-(tert-butyldiphenylsilyloxy)-3.4-(dimethylmethylenedioxy)-9-(4-methoxybenzyloxy)-7-(methoxymethoxy)-5-decene 
• 851278-42-7 (1S,2E,4S,5S,2'R)-7-[(tert-butyldiphenylsilyl)oxy]-4,5-dihydroxy-1-[2'-[(4-methoxybenzyl)oxy]propyl]-2-heptenyl acetate 
• 929117-85-1 (E)-(3S,5R)-1-{(4S,5S)-5-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-5-(4-methoxy-benzyloxy)-hex-1-en-3-ol 
• 851278-41-6 (3S,4R,5S,6E)-1-(tert-butyldiphenylsilyloxy)-4,5-epoxy-9-(4-methoxybenzyloxy)-6-decen-3-ol 
• 851278-40-5 (3S,4Z,6E,9R)-1-[(tert-butyldiphenylsilyl)oxy]-9-[(4-methoxybenzyl)oxy]-4,6-decadien-3-ol 
• 851278-45-0 (1E)-5-[(tert-butyldiphenylsilyl)oxy]-1-trimethylsilyl-1-penten-3-ol 
• 851278-57-4 (1E,3S)-5-[(tert-butyldiphenylsilyl)oxy]-1-trimethylsilyl-1-penten-3-ol 

Downstream Products

• 127393-89-9 (4S,5S,8S,10R,E)-4,5,8-trihydroxy-10-methyl-4,5,9,10-tetrahydro-3H-oxecin-2(8H)-one 

Relevant academic research and scientific papers

Nickel-catalyzed coupling producing (2Z)-2,4-alkadien-1-ols, conversion to (E)-3-alkene-1,2,5-triol derivatives, and synthesis of decarestrictine D

The 3-alkene-1,2,5-triol structure is not only a major framework of biologically important molecules but also a new functional-group-rich unit for synthesis of polyols and sugars. A method furnishing such triol derivatives 8 was developed and successfully applied to synthesis of decarestrictine D (18). First, coupling reaction of the unprotected alcohols 2 with borates 4 was investigated to produce the dienyl alcohols 6 with NiCl2(dppf) in Et2O/THF (5:1) at room temperature. The hydroxyl-group-directed epoxidation of 6 followed by palladium-catalyzed reaction with AcOH (Scheme 1) furnished 3-alkene-1,2,5-triol derivatives 8. Since each step proceeded with high stereo- and regioselectivities, the stereochemistry of 8 has been correlated with the olefin geometry of 6. With the above transformation in mind, synthesis of the full carbon skeleton of decarestrictine D (18) could be designed easily and was completed successfully. Furthermore, a new seco acid 19b with the MOM protective group for the three hydroxyl groups was found to afford macrolide 48 in a yield higher than those reported previously.

Stereoselective synthesis of decarestrictine D from a previously inaccessible (2Z,4E)-alkadienyl alcohol precursor

(Chemical Equation Presented) The core structure of decarestrictine D was constructed by stereoselective oxygenation of (2Z,4E)-alkadienyl alcohol, which could be synthesized by a nickel-catalyzed coupling reaction between the corresponding cis bromide an

Synthesis of tuckolide, a new cholesterol biosynthesis inhibitor

Tuckolide (decarestrictine D), a 10-membered lactone isolated from P. corylophilum and polyporus tuberaster fungi that potently inhibits cholesterol biosynthesis, was synthesized. The key steps include a Sharpless catalytic asymmetric dihydroxylation reaction (AD) of the methoxymethyl (MOM) ether protected diene 2 and a direct Corey-Nicolaou lactonization reaction of seco-acid 1 with added silver perchlorate. The selectivity of the dihydroxylation step was found to be highly dependent on the nature of the protecting group adjacent to the diene in 2. The selectivity of the asymmetric dihydroxylation reaction of 2 indicates that both steric and electronic effects can lead to significant amounts of the undesired isomers. This synthesis establishes the absolute stereochemistry of tuckolide showing the C3 hydroxyl bearing carbon with an S-configuration comparable in an absolute sense to that in the lactone portion of the HMG-CoA reductase inhibitor compactin.