445424-76-0

Upstream product

• 50-00-0 formaldehyd 
• 75-24-1 trimethylaluminum 
• 91266-03-4 tert-butyl-pent-4-ynyloxy-diphenyl-silane 
• 215251-69-7 4-(tert-butyldiphenylsilyloxy)-N-methoxy-N-methylbutanamide 
• 131085-31-9 5-((tert-butyldiphenylsilyl)oxy)pentan-2-one 
• 445424-75-9 ethyl 6-(tert-butyldiphenylsilyloxy)-3-methylhex-2-enoate 

Downstream Products

• 1276069-79-4 (E)-6-((tert-butyldiphenylsilyl)oxy)-3-methylhex-2-enal 
• 1207538-89-3 C₂₅H₃₄O₂Si 
• 1207538-76-8 C₂₅H₃₆O₂Si 

Relevant academic research and scientific papers

Total synthesis, stereochemical reassignment, and biological evaluation of (-)-lyngbyaloside B

(-)-Lyngbyaloside B is a 14-membered macrolide glycoside isolated from the marine cyanobacterium Lyngbya sp. as a cytotoxic substance by Moore and co-workers. The first total synthesis of (-)-lyngbyaloside B and the reassignment of its stereostructure is described. The synthesis features an Abiko-Masamune aldol reaction, a vinylogous Mukaiyama aldol reaction, and a macrocyclization involving an acyl ketene intermediate for the construction of the macrocyclic backbone, which contains an acylated tertiary alcohol. The antiproliferative activity of selected compounds against a small panel of human cancer cell lines is also reported.

Catalytic Asymmetric Allylic Substitution with Copper(I) Homoenolates Generated from Cyclopropanols

By using copper(I) homoenolates as nucleophiles, which are generated through the ring-opening of 1-substituted cyclopropane-1-ols, a catalytic asymmetric allylic substitution with allyl phosphates is achieved in high to excellent yields with high enantioselectivity. Both 1-substituted cyclopropane-1-ols and allylic phosphates enjoy broad substrate scopes. Remarkably, various functional groups, such as ether, ester, tosylate, imide, alcohol, nitro, and carbamate are well tolerated. Moreover, the present method is nicely extended to the asymmetric construction of quaternary carbon centers. Some control experiments argue against a radical-based reaction mechanism and a catalytic cycle based on a two-electron process is proposed. Finally, the synthetic utilities of the product are showcased by means of the transformations of the terminal olefin group and the ketone group.

Total Synthesis and Complete Stereostructure of a Marine Macrolide Glycoside, (-)-Lyngbyaloside B

We have described in detail the total synthesis of both the proposed and correct structures of (-)-lyngbyaloside B, which facilitated the elucidation of the complete stereostructure of this natural product. Our study began with the total synthesis of 13-demethyllyngbyaloside B, in which an esterification/ring-closing metathesis (RCM) strategy was successfully used for the efficient construction of the macrocycle. We also established reliable methods for the introduction of the conjugated diene side chain and the l-rhamnose residue onto the macrocyclic framework. However, the esterification/RCM strategy proved ineffective for the parent natural product because of the difficulties in acylating the sterically encumbered C-13 tertiary alcohol; macrolactionization of a seco-acid was also extensively investigated under various conditions without success. We finally completed the total synthesis of the proposed structure of (-)-lyngbyaloside B by means of a macrolactonization that involves an acyl ketene as the reactive species. However, the NMR spectroscopic data of our synthetic material did not match those of the authentic material, which indicated that the proposed structure must be re-examined. Inspection of the NMR spectroscopic data of the natural product and molecular mechanics calculations led us to postulate that the configuration of the C-10, C-11, and C-13 stereogenic centers had been incorrectly assigned in the proposed structure. Finally, our revised structure of (-)-lyngbyaloside B was unambiguously verified through total synthesis.

Rhodium-catalyzed endo -selective epoxide-opening cascades: formal synthesis of (-)-brevisin

[Rh(CO)2Cl]2 is as an effective catalyst for endo-selective cyclizations and cascades of epoxy-(E)-enoate alcohols, thus enabling the synthesis of oxepanes and oxepane-containing polyethers from di- and trisubstituted epoxides. Synth

Efficient one-to-one coupling of easily available 1,3-dienes with carbon dioxide

An efficient one-to-one coupling reaction of atmospheric pressure carbon dioxide with 1,3-dienes is realized for the first time through PSiP-pincer type palladium-catalyzed hydrocarboxylation. The reaction is applicable to various 1,3-dienes including easily available chemical feedstock such as 1,3-butadiene and isoprene. This protocol affords a highly useful method for the synthesis of β,γ-unsaturated carboxylic acid derivatives from CO2.

Synthetic studies toward neovibsanins A and B: construction of the neovibsanin core utilizing palladium(0)-catalyzed carbonylative cyclization with carbon monoxide

The core A-ring of neovibsanins A (1) and B (2), which are potent neurotrophic agents isolated from the leaves of Viburnum awabuki, have been effectively constructed by the intramolecular palladium(0)-catalyzed carbonylative cyclization of alkenyl iodide

Diastereoselective ring-closing metathesis for the construction of a quaternary carbon stereogenic center

A diastereoselective ring-closing metathesis of the trienes 1 leading to the formation of a quaternary carbon stereogenic center on the cyclohexenes 2 has been developed.