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Total Synthesis of Bryostatin 8 Using an Organosilane-Based Strategy.
Convergent total synthesis of bryostatin 8 has been accomplished by an organosilane-based strategy, efficiently joining the northern and southern parts of the molecule.
TMSBr/InBr3-promoted Prins cyclization/homobromination of dienyl alcohol with aldehyde to construct cis-THP containing an exocyclic E-alkene.
A TMSBr/InBr3-promoted Prins cyclization/homobromination reaction of dienyl alcohol with aldehyde has been developed to construct a unique cis-E THP shown as the A ring in (-)-exiguolide and the B
Total Synthesis of Bryostatin 8 and (–)-Exiguolide: Applications of an Organosilane Strategy
In this Account, we give an overview of our recent efforts towards the total synthesis of two marine natural products: bryostatin 8 and (–)-exiguolide. The central theme is to highlight the power of
[1,5]-Anion relay/[2,3]-Wittig rearrangement of 3,3-bis(silyl) allyl enol ethers: synthesis of useful vinyl bis(silane) species.
The [1,5]-anion relay/[2,3]-Wittig rearrangement of 3,3-bis(silyl) enol allyl ethers has been developed. This reaction provides an efficient method to synthesize versatile vinyl bissilanes, which can
Addition of TMS-substituted oxiranyl anions to acylsilanes. A highly stereoselective approach to tetrasubstituted (Z)-β-hydroxy-α-TMS silyl enol ethers.
A highly stereoselective approach to novel tetrasubstituted (Z)-β-hydroxy-α-TMS silyl enol ethers is described. The reaction proceeds via a sequential addition/[1,2]-Brook
Ipomoeassin F Binds Sec61α to Inhibit Protein Translocation
Ipomoeassin F is a potent natural cytotoxin that inhibits growth of many tumor cell lines with single-digit nanomolar potency. However, its biological and pharmacological properties have remained
Geminal bis(silyl) enal: a versatile scaffold for stereoselective synthesizing C3,O1-disilylated allylic alcohols based upon anion relay chemistry.
Geminal bis(silyl) enal 2a is shown to be a useful scaffold for anion relay chemistry (ARC) aimed at the stereoselective synthesis of C(3),O(1)-disilylated allylic alcohols. The ARC reaction is
[1,4]-S- to O-silyl migration: multicomponent synthesis of α-thioketones through chemoselective transformation of esters to ketones with organolithium reagents.
A [1,4]-S- to O-silyl migration has been exploited to chemoselectively transform esters into ketones by using organolithium reagents, allowing multicomponent synthesis of α-thioketones, valuable building blocks for the synthesis of cyclic or multifunctionalized organosulfur compounds.
[1,5]-Anion relay via intramolecular proton transfer to generate 3,3-bis(silyl) allyloxy lithium: a useful scaffold for syn-addition to aldehydes and ketones.
A [1,5]-anion relay has been achieved in 3,3-bis(silyl) benzyl enol ether and this endo-oriented allyl anion is stable at -78 °C and undergoes diastereoselective syn-addition at the γ-position with aldehydes and ketones to give monobenzyl-substituted 1,2-diols.