Protecting group free enantiospecific total syntheses of structurally diverse natural products of the tetrahydrocannabinoid family.

@article{Dethe2015ProtectingGF,
  title={Protecting group free enantiospecific total syntheses of structurally diverse natural products of the tetrahydrocannabinoid family.},
  author={Dattatraya H. Dethe and Rohan D Erande and Samarpita Mahapatra and Saikat Das and Vijaya Kumar B},
  journal={Chemical communications},
  year={2015},
  volume={51 14},
  pages={
          2871-3
        }
}
A simple, highly diastereoselective, Lewis acid catalyzed Friedel-Crafts coupling of a cyclic allylic alcohol with resorcinol derivatives has been developed. The method was applied for the enantiospecific total syntheses of structurally diverse natural products such as machaeriol-D, Δ(8)-THC, Δ(9)-THC, epi-perrottetinene and their analogues. Synthesis of both natural products and their enantiomers has been achieved with high atom economy, in a protecting group free manner and in less than 6… Expand
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References

SHOWING 1-10 OF 44 REFERENCES
Stereoselective total synthesis of (-)-perrottetinene and assignment of its absolute configuration.
TLDR
The first stereoselective total synthesis of the bibenzyl tetrahydrocannabinol, (-)-perrottetinene, has been achieved from readily available starting materials using a chiral gamma-hydroxy vinylstannane. Expand
Enantioselective total synthesis of (+)-conicol via cascade three-component organocatalysis.
TLDR
Through this work, the absolute configuration of (+)-conicol was thereby elucidated and structures of the three-component domino reaction adducts, 20 and 21, including their absolute configurations, were confirmed unambiguously by X-ray analysis. Expand
Synthesis of (-)-Delta9-trans-tetrahydrocannabinol: stereocontrol via Mo-catalyzed asymmetric allylic alkylation reaction.
[reaction: see text] Delta9-THC is synthesized in enantiomericaly pure form, where all of the stereochemistry is derived from the molybdenum-catalyzed asymmetric alkylation reaction of the extremelyExpand
Synthesis of tetrahydrocannabinols based on an indirect 1,4-addition strategy.
TLDR
An indirect method consisting of iodination of the cyclohexenones at the alpha position and reaction of the alpha-iodo-beta-aryl-cylohexanones with EtMgBr to generate magnesium enolates showed a high reactivity toward ClP(O)(OEt)(2) to furnish enol phosphates. Expand
A method to accomplish a 1,4-addition reaction of bulky nucleophiles to enones and subsequent formation of reactive enolates.
TLDR
BF(3)-promoted 1,4-addition of bulky aryl groups to alpha-iodo enones, prepared from the parent enone, afforded beta-aryl-alpha-iodi ketones, which was applied successfully to a synthesis of Delta(1)-trans-tetrahydrocannabinol. Expand
Enantioselective total synthesis of (-)-Δ8-THC and (-)-Δ9-THC via catalytic asymmetric hydrogenation and S(N)Ar cyclization.
TLDR
The highly efficient asymmetric total syntheses of (-)-Δ(8)-tetrahydrocannabinol (THC) and (-)- Δ(9-THC (14 steps, 30%) have been developed by using ruthenium-catalyzed asymmetric hydrogenation of racemic α-aryl cyclic ketones via dynamic kinetic resolution and intramolecular S(N)Ar cyclization. Expand
Cationic bis(oxazoline)Cu(II) lewis acid catalysts. Application to the asymmetric synthesis of ent-Δ1-tetrahydrocannabinol
Abstract The Diels-Alder reaction of acryloyl oxazolidinone and 1-acetoxy-3-methylbutadiene is catalyzed by the cationic bis(oxazoline)Cu(II) complex 4 in high enantioselectivity. The cycloadduct isExpand
An efficient ring-closing metathesis reaction of geminally disubstituted olefins using first generation Grubbs’ catalyst: enantiospecific synthesis of pacifigorgianes
Abstract An efficient ring closing metathesis reaction with first generation Grubbs’ catalyst [PhCHRuCl 2 (PCy 3 ) 2 ] involving geminally disubstituted olefins has been discovered. It has beenExpand
Bisabosquals, novel squalene synthase inhibitors. II. Physico-chemical properties and structure elucidation.
The squalene synthase inhibitor bisabosqual A was isolated from the culture broth of Stachybotrys sp. RF-7260, and its structure was determined on the basis of spectroscopic methods includingExpand
Tetrahydrocannabinols by terpenylation of olivetol with (+)-trans-2- and -3-carene epoxides
Abstract Re-examination of the acid-catalysed terpenylation of olivetol by (+)- trans -2-carene epoxide shows that cannabidiols, as well as tetrahydrocannabinols, are produced, necessitating aExpand
...
1
2
3
4
5
...