Synthesis of Polysubstituted Tetrahydropyrans by Stereoselective Hydroalkoxylation of Silyl Alkenols: En Route to Tetrahydropyranyl Marine Analogues

Tetrahydropyrans are abundantly found in marine natural products. The interesting biological properties of these compounds and their analogues make necessary the development of convenient procedures for their synthesis. In this paper, an atom economy access to tetrahydropyrans by intramolecular acid-mediated cyclization of silylated alkenols is described. p-TsOH has shown to be an efficient reagent to yield highly substituted tetrahydropyrans. Moreover, excellent diastereoselectivities are obtained both for unsubstituted and alkylsubstituted vinylsilyl alcohols. The methodology herein developed may potentially be applied to the synthesis of marine drugs derivatives.

• Publication year

  2018

• Venue

  Marine Drugs

• Publication date

  2018-11-01

• Fields of study

  Biology, Medicine, Chemistry

• Identifiers
  DOI 10.3390/md16110421PMID 30388761PMCID 6265778
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Investigation and mechanistic study into intramolecular hydroalkoxylation of unactivated alkenols catalyzed by cationic lanthanide complexes

  2017cited by this paper
• From Silylated Trishomoallylic Alcohols to Dioxaspiroundecanes or Oxocanes: Catalyst and Substitution Influence.

  2016cited by this paper
• Efficient access to polysubstituted tetrahydrofurans by electrophilic cyclization of vinylsilyl alcohols

  2015cited by this paper
• Competitive silyl-Prins cyclization versus tandem Sakurai-Prins cyclization: an interesting substitution effect.

  2014cited by this paper
• Synthesis of Saturated Oxygenated Heterocycles I: 5- and 6-Membered Rings

  2014cited by this paper
• Efficiency of Acid‐ and Mercury‐Catalyzed Cyclization Reactions in the Synthesis of Tetrahydrofurans from Allylsilyl Alcohols

  2012cited by this paper
• Intramolecular hydroalkoxylation in Brønsted acidic ionic liquids and its application to the synthesis of (±)-centrolobine.

  2011cited by this paper
• Efficient intramolecular hydroalkoxylation of unactivated alkenols mediated by recyclable lanthanide triflate ionic liquids: scope and mechanism.

  2010cited by this paper
• Synthesis of six-membered oxygenated heterocycles through carbon-oxygen bond-forming reactions

  2008cited by this paper
• Total synthesis of platensimycin.

  2006cited by this paper
• Hydroamination and hydroalkoxylation catalyzed by triflic acid. Parallels to reactions initiated with metal triflates.

  2006cited by this paper
• Biomimetic synthesis of acid-sensitive (-)- and (+)-caparrapi oxides, (-)- and (+)-8-epicaparrapi oxides, and (+)-dysifragin induced by artificial cyclases.

  2005cited by this paper
• Silylcuprates from allene and their reaction with alpha,beta-unsaturatedd nitriles and imines. Synthesis of silylated oxo compounds leading to cyclopentane and cycloheptane ring formation.

  2005cited by this paper
• Catalytic formation of C-O bonds by alkene activation: Lewis acid-cycloisomerisation of olefinic alcohols.

  2005cited by this paper
• Spiro-cyclopropanation from oxoallylsilanes.

  2005cited by this paper
• Ruthenium catalyzed addition reaction of carboxylic acid across olefins without beta-hydride elimination.

  2004cited by this paper
• Ruthenium Catalyzed Addition Reaction of Carboxylic Acid Across Olefins Without β-Hydride Elimination.

  2004cited by this paper
• Triflic acid-catalysed cyclisation of unsaturated alcohols

  2004cited by this paper
• Acid-catalyzed cyclization of epoxyallylsilanes. An unusual rearrangement cyclization process.

  2003cited by this paper
• Chlorosulfonic acid as a convenient electrophilic olefin cyclization agent

  2003cited by this paper
• Lewis Base-Catalyzed Addition of Trialkylaluminum Compounds to Epoxides

  2001cited by this paper
• Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy Group: A New Method for Stereoselective Synthesis of Disubstituted Tetrahydrofurans1

  2000cited by this paper
• NOVEL NORSESTERTERPENES, WHICH INHIBIT GASTRULATION OF THE STARFISH EMBRYO, FROM THE MARINE SPONGE RHOPALOEIDES SP.

  1998cited by this paper
• Stereoselective synthesis of a 2,2,5-trisubstituted tetrahydropyran chiron via 1,3- and 1,6-asymmetric induction: A total synthesis of (−)-malyngolide

  1998cited by this paper
• Stereochemical Control in Organic Synthesis Using Silicon-Containing Compounds.

  1997cited by this paper
• SILICON-DIRECTED CYCLIZATION OF VINYLSILANES BEARING HYDROXY GROUP CATALYZED BY AN ACID

  1995influential reference
• The phenyldimethylsilyl group as a masked hydroxy group

  1995cited by this paper
• Stereocontrolled construction of substituted pyrrolidines based on intramolecular protodesilylation reaction. Enantiospecific synthesis of (–)-kainic acid and (+)-allokainic acid from L-serine

  1993cited by this paper
• Stereocontrol in organic synthesis using silicon compounds

  1988cited by this paper
• Staggered models for asymmetric induction: attack trajectories and conformations of allylic bonds from ab initio transition structures of addition reactions

  1982cited by this paper
• Structure and absolute configuration of malyngolide, an antibiotic from the marine blue-green alga Lyngbya majuscula Gomont

  1980cited by this paper

• An asymmetric Salamo-based Zn complex supported on Fe3O4 MNPs: a novel heterogeneous nanocatalyst for the silyl protection and deprotection of alcohols under mild conditions

  2021cites this paper
• Recent advances in catalytic silylation of hydroxyl‐bearing compounds: A green technique for protection of alcohols using Si–O bond formations

  2020cites this paper
• Intramolecular Cyclization of Alkenyl Alcohols: Towards the Synthesis of Oxacycles

  2020cites this paper