77412-05-6

Upstream product

• 4548-78-1 (3-methylbutyl)magnesium bromide 
• 107-19-7 propargyl alcohol 
• 77412-12-5 5-methyl-2-(phenylthio)-2-(trimethylsilylmethyl)hexanal 
• 77412-11-4 5-methyl-2-(phenylthio)-2-(trimethylsilylmethyl)hexanenitrile 
• 541-28-6 isopentyl iodide 
• 632357-72-3 1-(tert-butyl-dimethyl-silanyloxy)-5-methyl-hexan-2-ol 
• 632358-01-1 1-(tert-butyl-dimethyl-silanyloxy)-5-methyl-hexan-2-one 
• 870-63-3 prenyl bromide 
• 22539-80-6 diethyl (3-methylbut-2-enyl)malonate 
• 628-46-6 5-methylhexanoic acid 
• 1860-39-5 5-methylhexanal 
• 936642-42-1 N-methoxy-N,5-dimethylhexanamide 
• 5398-08-3 diethyl isopentylmalonate 
• 632358-09-9 tert-butyl-dimethyl-[2-(3-methyl-butyl)-allyloxy]-silane 

Downstream Products

• 936642-43-2 C₁₉H₂₆O₄ 
• 632357-89-2 2-(tert-butyl-dimethyl-silanyloxy)-4-(1-phenyl-1H-tetrazol-5-ylsulfanyl)-butyric acid 2-(3-methyl-butyl)-allyl ester 
• 398517-19-6 2-(tert-butyl-dimethyl-silanyloxy)-4-(1-phenyl-1H-tetrazole-5-sulfonyl)-butyric acid 2-(3-methyl-butyl)-allyl ester 
• 398517-13-0 2-(tert-butyl-dimethyl-silanyloxy)-4-(1-phenyl-1H-tetrazole-5-sulfonyl)-butyric acid 2-(3-methyl-butyl)-allyl ester 
• 1521266-97-6 C₃₆H₅₀O₃PSi⁽¹⁺⁾*Br^(1-) 

Relevant academic research and scientific papers

Total Synthesis of (-)-Lasonolide A

The lasonolides are novel polyketides that have displayed remarkable biological activity in vitro against a variety of cancer cell lines. Herein we describe our first-generation approach to the formal synthesis of lasonolide A. The key findings from these studies ultimately allowed us to go on and complete a total synthesis of lasonolide A. The convergent approach unites two highly complex fragments utilizing a Ru-catalyzed alkene-alkyne coupling. This type of coupling typically generates branched products; however, through a detailed investigation, we are now able to demonstrate that subtle structural changes to the substrates can alter the selectivity to favor the formation of the linear product. The synthesis of the fragments features a number of atom-economical transformations which are highlighted by the discovery of an engineered enzyme to perform a dynamic kinetic reduction of a β-ketoester to establish the absolute stereochemistry of the southern tetrahydropyran ring with high levels of enantioselectivity.

A concise synthesis of (-)-lasonolide A

Lasonolide A is a novel polyketide displaying potent anticancer activity across a broad range of cancer cell lines. Here, an enantioselective convergent total synthesis of the (-)-lasonolide A in 16 longest linear and 34 total steps is described. This approach significantly reduces the step count compared to other known syntheses. The synthetic strategy utilizes alkyne-bearing substrates as core building blocks and is highlighted by stitching together two similarly complex halves via a key Ru-catalyzed alkene-alkyne coupling and macrolactionization.

Enantioselective total synthesis of macrolide antitumor agent (-)-lasonolide A

Equation presented An enantioselective total synthesis of (-)-lasonolide A is described. The upper tetrahydropyran ring was constructed stereoselectively by an intramolecular 1,3-dipolar cycloaddition reaction. The bicyclic isooxazoline led to the tetrahy

A novel synthesis of the north west portion of Lasonolide A - An anticancer macrolide using Claisen rearrangement

A simplified analogue of Lasonolide A (C23-C35 side chain) was synthesized using Fujisawa's stereoselective variant of the Ireland Claisen ester rearrangement.

Lasonolide A: Structural revision and total synthesis

The proposed structure of lasonolide A was synthesized employing radical cyclization reactions of β-alkoxyacrylates for preparation of the tetrahydropyranyl units A and B, but the spectroscopic data did not match those of the natural product. Both enantio

Lasonolide A: Structural revision and synthesis of the unnatural (-)-enantiomer

Total synthesis of the unnatural (-)-enantiomer of lasonolide A was achieved starting from ethyl l-malate. The two tetrahydropyranyl fragments were prepared stereoselectively via radical cyclization reactions of β-alkoxyacrylates. The full structure of na

The Formation of Allyl Sulphides by Phenylthio-migration: Control by Silicon

When γ-silyl-β-phenylthio-alcohols are treated with acid, the strategically placed silyl group encourages the rearrangement of the phenylthio-group, both from a secondary migration origin to a secondary migration terminus, and from a secondary migration origin to a tertiary migration terminus (4)->(6).Geraniol/nerol (12) and linalool (14) have been synthesised from a common intermediate (11) using this type of reaction.Phenylthio-migration from a tertiary migration origin (17)->(3) can be controlled to a limited extent by a suitably placed silyl group, but it is easier to achieve direct β-elimination of the silyl and phenylthio-groups (17)->(18).