76382-80-4Relevant articles and documents
Regio- And Stereoselective (S N2) N -, O -, C - And S -Alkylation Using Trialkyl Phosphates
Banerjee, Amit,Hattori, Tomohiro,Yamamoto, Hisashi
, (2021/06/16)
Bimolecular nucleophilic substitution (S N 2) is one of the most well-known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable, which makes them problematic for laboratory use. In contrast, trialkyl phosphates are inexpensive, readily accessible and stable at room temperature, under air, and are easy to handle, but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various N -, O -, C - and S -nucleophiles using readily available trialkyl phosphates. The reaction proceeds smoothly in excellent yield, and quantitative yield in many cases, and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to 98% ee).
Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals
Kyasa, ShivaKumar,Meier, Rebecca N.,Pardini, Ruth A.,Truttmann, Tristan K.,Kuwata, Keith T.,Dussault, Patrick H.
, p. 12100 - 12114 (2016/01/09)
Although transfer of electrophilic alkoxyl ("RO+") from organic peroxides to organometallics offers a complement to traditional methods for etherification, application has been limited by constraints associated with peroxide reactivity and stability. We now demonstrate that readily prepared tetrahydropyranyl monoperoxyacetals react with sp3 and sp2 organolithium and organomagnesium reagents to furnish moderate to high yields of ethers. The method is successfully applied to the synthesis of alkyl, alkenyl, aryl, heteroaryl, and cyclopropyl ethers, mixed O,O-acetals, and S,S,O-orthoesters. In contrast to reactions of dialkyl and alkyl/silyl peroxides, the displacements of monoperoxyacetals provide no evidence for alkoxy radical intermediates. At the same time, the high yields observed for transfer of primary, secondary, or tertiary alkoxides, the latter involving attack on neopentyl oxygen, are inconsistent with an SN2 mechanism. Theoretical studies suggest a mechanism involving Lewis acid promoted insertion of organometallics into the O-O bond.
A highly efficient method for the reductive etherification of carbonyl compounds with triethylsilane and alkoxytrimethylsilane catalyzed by iron(III) chloride
Iwanami, Katsuyuki,Seo, Hana,Tobita, Yuki,Oriyama, Takeshi
, p. 183 - 186 (2007/10/03)
Facile reductive etherification of carbonyl compounds can be conveniently performed by reaction with triethylsilane and alkoxytrimethylsilane catalyzed by iron(III) chloride. The corresponding alkyl ethers, including benzyl and allyl ethers, of the reduced alcohols were obtained in good to excellent yields under mild reaction conditions.