Synthesis of 1,1′-Diarylethanes and Related Systems by Displacement of Trichloroacetimidates with Trimethylaluminum

Mahajani, Nivedita; Chisholm, John D.

doi:10.1021/acs.joc.8b00027

Cited by 8 publications

(2 citation statements)

References 102 publications

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“…The methyl-2,2,2-trichloroacetimidate 10 , ethyl-2,2,2-trichloroacetimidate 11 , t -butyl-2,2,2-trichloroacetimidate 13 , allyl-2,2,2-trichloroacetimidate 14 , and benzyl-2,2,2-trichloroacetimidate 17 used in these studies were purchased from commercial sources. Cyclohexyl-2,2,2-trichloroacetimidate 12 , prenyl-2,2,2-trichloroacetimidate 15 , propargyl-2,2,2-trichloroacetimidate 16 , (2,4,6-trimethylphenyl)methyl-2,2,2-trichloroacetimidate 18 , (4-methoxyphenyl)methyl-2,2,2-trichloroacetimidate 20 , (3,4-dimethoxoxyphenyl)methyl-2,2,2-trichloroacetimidate 22 , (4-nitrophenyl)methyl-2,2,2-trichloroacetimidate 23 , furfuryl-2,2,2-trichloroacetimidate 24 , 1-phenethyl-2,2,2-trichloroacetimidate 25 , , diphenylmethyl-2,2,2-trichloroacetimidate 26 , , and (2-methoxyphenyl)phenylmethyl-2,2,2-trichloroacetimidate 29 were synthesized as previously reported.…”

Section: Methodsmentioning

confidence: 99%

Ester Formation via Symbiotic Activation Utilizing Trichloroacetimidate Electrophiles

et al. 2019

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Trichloroacetimidates are useful reagents for the synthesis of esters under mild conditions that do not require an exogenous promoter. These conditions avoid the undesired decomposition of substrates with sensitive functional groups that are often observed with the use of strong Lewis or Brønsted acids. With heating, these reactions have been extended to benzyl esters without electron donating groups. These inexpensive and convenient methods should find application in the formation of esters in complex substrates.

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Section: Methodsmentioning

confidence: 99%

Ester Formation via Symbiotic Activation Utilizing Trichloroacetimidate Electrophiles

et al. 2019

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“…17 More recently the first displacement of an imidate with an alkylmetal reagent (trimethylaluminum) was reported, although in most cases this also required a Lewis acid promoter to achieve good yields. 18 In this study the direct C–C bond formation of benzylic trichloroacetimidates with a stable carbon nucleophile (allyltributylstannanes) is investigated, with the premise that it will lead to a new method to access 1,1′-diarylbutyl groups under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Promoter free allylation of trichloroacetimidates with allyltributylstannanes under thermal conditions to access the common 1,1′-diarylbutyl pharmacophore

Mahajani

Chisholm

2018

Org. Biomol. Chem.

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1,1'-Diarylbutyl groups are a common pharmacophore found in many biologically active small molecules. To access these systems under mild conditions, the reaction of diarylmethyl trichloroacetimidates with allyltributylstannanes was explored. Simply heating allyltributylstannane with the trichloroacetimidate resulted in substitution of the imidate with an allyl group. Unlike other methods used to access these systems, no strong base, transition metal catalyst, Brønsted acid or Lewis acid promoter was required to affect the transformation. Conversions are best with electron rich benzylic trichloroacetimidate systems, where excellent yields are achieved just by refluxing the reactants together in nitromethane.

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Carbon–Carbon Bond Forming Reactions of Vinyl Cations: A Personal Perspective

Riu,

Popov,

Wigman

et al. 2024

Eur J Org Chem

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Vinyl cations were first proposed as reactive intermediates nearly eighty years ago by Jacobs, and their properties were closely studied in the second half of the twentieth century by Stang, Olah, Caple, Grob, Hanack, and others. Recent developments in the catalytic generation and reactions of vinyl cations with unactivated C(sp3) −H bonds prompted us to assemble a field guide based on our previous experiences that is geared for synthetic chemists who are looking to construct C−C bonds via vinyl cation C−H insertion or Friedel‐Crafts addition. In particular, this article focuses on silylium‐ and lithium‐initiated C−C bond forming reactions of vinyl cations generated from vinyl triflates and ultimately aims to provide the reader with context and accelerate their selection of optimal reaction conditions and starting materials.

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Synthesis of 1,1′-Diarylethanes and Related Systems by Displacement of Trichloroacetimidates with Trimethylaluminum

Cited by 8 publications

References 102 publications

Ester Formation via Symbiotic Activation Utilizing Trichloroacetimidate Electrophiles

Ester Formation via Symbiotic Activation Utilizing Trichloroacetimidate Electrophiles

Promoter free allylation of trichloroacetimidates with allyltributylstannanes under thermal conditions to access the common 1,1′-diarylbutyl pharmacophore

Carbon–Carbon Bond Forming Reactions of Vinyl Cations: A Personal Perspective

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