Ring-closing metathesis of allylsilanes as a flexible strategy toward cyclic terpenes. short syntheses of teucladiol, isoteucladiol, poitediol, and dactylol and an attempted synthesis of caryophyllene.

  title={Ring-closing metathesis of allylsilanes as a flexible strategy toward cyclic terpenes. short syntheses of teucladiol, isoteucladiol, poitediol, and dactylol and an attempted synthesis of caryophyllene.},
  author={Matthew S. Dowling and Christopher D. Vanderwal},
  journal={The Journal of organic chemistry},
  volume={75 20},
The development of a strategy consisting of allylsilane ring-closing metathesis and subsequent S(E)' electrophilic desilylation (allylsilane RCM/S(E)') to construct exo-methylidenecycloalkanes is described. Its utility is documented in short syntheses of teucladiol and poitediol. A key transformation in the synthesis of teucladiol is an aldol addition that establishes three stereochemical relationships in one step with ≥10:1 diastereoselectivity and provides a fascinating example of double… 

Ring‐Closing Metathesis of Allylsilanes as a Flexible Strategy Toward Cyclic Terpenes. Short Syntheses of Teucladiol, Isoteucladiol, Poitediol, and Dactylol and an Attempted Synthesis of Caryophyllene.

Ring-closing metathesis of the allylsilane (I) followed by methylation and desilylation allows a short route to teucladiol (V) and isoteucladiol (VI).

A short enantioselective total synthesis of (-)-englerin A.

An enantioselective total synthesis of guaiane sesquiterpene A that allows the construction of this bioactive compound in a few preparatively simple steps is reported.

Enantioselective Total Synthesis of (+)-Psiguadial B.

The first enantioselective total synthesis of the cytotoxic natural product (+)-psiguadial B is reported, using a ring-closing metathesis to build the bridging bicyclo- terpene framework.

Bicyclo [6.3.0] Undecane Sesquiterpenoids: Structures, Biological Activities, and Syntheses

This review focuses on natural sesquiterpenoids and their biological activities and synthesis, and aims to provide a foundation for further research of these interesting compounds.

Recent Advances in the Total Synthesis of Natural Products Containing Eight-Membered Carbocycles (2009-2019).

This review illustrates the diversity and creativity in the elegant synthetic designs of eight-membered carbocycles in natural products with cyclooctane moieties and provides timely illumination and beneficial guidance for future synthetic efforts for organic chemists who are interested in this area.

Enyne-2-pyrone [4 + 4]-Photocycloaddition: Sesquiterpene Synthesis and a Low-Temperature Cope Rearrangement.

Intramolecular photoreaction of 2-pyrones with a 1,3-enyne yields an unstable 1,2,5-cyclooctatriene product, and Cope rearrangement yields a nine-membered ring fused to a cyclobutane.

p-Anisaldehyde-Photosensitized Sulfonylcyanation of Chiral Cyclobutenes: Enantioselective Access to Cyclic and Acyclic Systems Bearing All-Carbon Quaternary Stereocenters.

The photosensitized p-anisaldehyde-mediated addition of sulfonylcyanides onto the π-system of cyclobutenes is shown to afford highly functionalized cyclobutanes in high yields and diastereocontrol.

Recent advances in the synthesis of gem-dimethylcyclobutane natural products.

This review highlights recent syntheses in which the gem-dimethylcyclobutane is assembled via de novo approaches and an outlook on the future of this research area is provided.

Synthesis of Chiral Cyclopentenones.

This Review provides an overview of reported methods for enantioselective and asymmetric syntheses of cyclopentenones, including chemical and enzymatic resolution, asymmetric synthesis via Pauson-Khand reaction, Nazarov cyclization and organocatalyzed reactions, asymmetrical functionalization of the existing cyclopENTenone unit, andfunctionalization of chiral building blocks.