6540-98-3

Usage

Synthesis Reference(s)

Synthesis, p. 520, 1979 DOI: 10.1055/s-1979-28738Tetrahedron Letters, 27, p. 65, 1986 DOI: 10.1016/S0040-4039(00)83941-6

Upstream product

• 539-82-2 ethyl n-valerate 
• 7433-56-9 (E)-5-decene 
• 6838-62-6 5,6-bis-trimethylsilanyloxy-dec-5-ene 
• 109-72-8 n-butyllithium 
• 201230-82-2 carbon monoxide 
• 110-62-3 pentanal 
• 1942-46-7 5-decyne 
• 7433-78-5 cis-5-decene 
• 108-94-1 cyclohexanone 
• 104925-69-1 (2,3-Dibutyl-oxiranyl)-diethoxy-methyl-silane 
• 624-24-8 methyl valerate 
• 84298-28-2 1H-1,2,3-benzotriazol-1-yl(n-butyl)methanone 
• 78-94-4 methyl vinyl ketone 
• 107-13-1 acrylonitrile 

Downstream Products

• 109-52-4 valeric acid 
• 5579-73-7 decane-5,6-dione 

Relevant academic research and scientific papers

Highly chemoselective direct crossed aliphatic-aromatic acyloin condensations with triazolium-derived carbene catalysts

It has been shown for the first time that triazolium precatalysts promote (in the presence of base) highly chemoselective crossed acyloin condensation reactions between aliphatic and ortho-substituted aromatic aldehydes. An o-bromine atom can serve as a temporary directing group to ensure high chemoselectivity (regardless of the nature of the other substituents on the aromatic ring) which then can be conveniently removed. The process is of broad scope and is operationally simple as it does not require the preactivation of any of the coupling partners to ensure selectivtiy. Preliminary data indicate that highly enantioselective variants of the reaction are feasible using chiral precatalysts.

BIOFUEL PRODUCTION

Methods, enzymes, recombinant microorganism, and microbial systems are provided for converting polysaccharides, such as those derived from biomass, into suitable monosaccharides or oligosaccharides, as well as for converting suitable monosaccharides or oligosaccharides into commodity chemicals, such as biofuels. Commodity chemicals produced by the methods described herein are also provided. Commodity chemical enriched, refinery-produced petroleum products are also provided, as well as methods for producing the same.

Efficient method for the deprotection of tert-butyldimethylsilyl ethers with TiCl4-Lewis base complexes: Application to the synthesis of 1β-methylcarbapenems

TiCl4-Lewis base (AcOEt, CH3NO2) complexes smoothly deprotected tert-butyldimethylsilyl (TBDMS) ethers. The reaction velocity with these complexes, which seemed less reactive due to the influence of Lewis bases, was considerably greater than that with TiCl4 alone. Selective desilylations between aliphatic and aromatic TBDMS ethers (1 and 5), between 1 and benzyl, allyl, tosyl, methoxyphenyl, and chloroacetyl ethers (13, 14, 15, 16, and 17), and between TBDMS and TBDPS ethers (18 and 19) were successfully performed. Desilylation of TBDMS-aldol, acyloin, and β-lactam analogues 9-12 proceeded smoothly due to anchimeric assistance by the neighboring carbonyl groups. The present method was successfully applied to the practical synthesis of 1β-methylcarbapenems 20a′-f′.

Stetter reaction in room temperature ionic liquids and application to the synthesis of haloperidol

Imidazolium-type room temperature ionic liquids (RTILs) have been used for the Stetter reaction, affording the desired 1,4-dicarbonyl compounds in good yields. Thiazolium salts and Et3N are efficient catalysts for this reaction performed in ionic liquid. The possibility to recycle and reuse the solvent has been demonstrated, although it was not possible to recycle the thiazolium catalyst. This method was used in the total synthesis of haloperidol.

The RuO4-catalyzed ketohydroxylation. Part 1. Development, scope, and limitation

A new straightforward oxidation of C,C-double bonds to unsymmetrical α-hydroxy ketones using catalytic amounts of RuCl3 and stoichiometric amounts of Oxone under buffered conditions has been developed, a reaction for which we coined the expression "ketohydroxylation". The transformation allows the direct formation of α-hydroxy ketones (acyloins) from olefins without intermediate formation of syn-diols. The present paper will provide detailed information starting with the underlying concept and the subsequent development of the reaction. The effect of base, solvent stoichiometry, and temperature will be discussed resulting in an improved mechanistic model that might help to explain the influence of different reaction parameters on reactivity and selectivity in RuO4-catalyzed oxidations of C,C-double bonds. Furthermore, an improved workup procedure allows the recovery of the ruthenium catalyst by precipitation while simplifying the overall product purification. The second part of the paper focuses on exploration of scope and limitation. A variety of substituted olefins are oxidized to α-hydroxy ketones in good to excellent regioselectivities and yield. Cyclic substrates proved to be problematic to oxidize; however, a careful analysis of temperature effects resulted in the development of a successful protocol for the ketohydroxylation of cyclic substrates by simply decreasing the reaction temperature.

Samarium diiodide promoted formation of 1,2-diketones and 1-acylamido-2-substituted benzimidazoles from N-acylbenzotriazoles

N-Acylbenzotriazoles, when treated with samarium diiodide in THF, undergo self-coupling reaction to afford 1,2-diketones in good to excellent yields; while when treated with samarium diiodide in CH3CN, they undergo ring-opening reaction to afford 1-acylamido-2-alkyl (or aryl) benzimidazoles in reasonable to good yields. A plausible mechanism was suggested.

RuO4-catalyzed ketohydroxylation of olefins

A new mild method for the oxidation of a variety of olefins to α-hydroxy ketones is described. Using the concept of a nucleophilic reoxidant, different olefins were ketohydroxylated with high regioselectivity in good to excellent yields.

Formation of 1,2-diketones by samarium diiodide promoted reaction of N-acylbenzotriazoles

Transformation of N-acylbenzotriazoles 1 into 1,2-diketones 2 in good to excellent yields has been realized by the use of samarium diiodide at room temperature.

Difluoroboroxymolybdenum fischer carbene complexes as precursors of acyl radicals: Dimerization and trapping with electron-deficient alkenes

Pentacarbonyl acyl molybdates 1 react with boron trifluoride to give difluoroboroxy Fischer carbene complexes 2, which undergo loss of the metal fragment at room temperature to form 1,2-diketones 3, 1,2-hydroxy ketones 4, or dimers 5 through a dimerization or decarbonylation-dimerization process of acyl radicals. Decomposition of 2 in the presence of electron-deficient alkenes 11 and 18 furnishes the two-, three-, and four-component coupling products 12, 13, 19, 20, and 21.

Convenient preparation of metals deposited on solid supports and their use in organic synthesis

'High-surface alkali metals' can be conveniently prepared via deposition of corresponding metals on various supports such as sodium chloride, polyethylene, polypropylene and cross-linked polystyrene from their solutions in liquid ammonia. Alkali metals deposited on polymeric supports can be stored in form of stable suspensions in inert solvents and used for the acyloin and Dieckmann condensations and for preparation of organolithiums. Addition of the suspension of supported alkali metal to a solution of zinc chloride gave an active zinc on polymeric support, which can be used for the Reformatski and Barbier reactions.