Cyclizations by carbon monoxide in Friedel-Crafts reactions. Facile synthesis of .beta.-disubstituted .alpha.-indanones

Bruson, Herman Alexander; Plant, Howard L.

doi:10.1021/jo01286a018

Cited by 16 publications

(1 citation statement)

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“…It became clear to us that a cost-effective synthesis of 1 must rely on construction of the requisite 4,5-disubstituted pyrimidine from inexpensive raw materials in a minimal number of unit operations. Since 2,2-dimethyl-1-indanone ( 6 ) had the potential of supplying the indane backbone of 1 at reasonable cost, our initial studies focused on this as the key starting material. Our strategy, depicted in Scheme , was to use the carbonyl of 6 as an electrophile in combination with a heteroatom-stabilized carbanion ( 8 ) to construct the carbon−carbon bond at what would eventually be the 5-position of the pyrimidine.…”

Section: Resultsmentioning

confidence: 99%

Process Chemistry Related to the Experimental Rice Herbicide 2,2-Dimethyl-1-(4-methylthio-5-pyrimidinyl)indane

Dietsche

Gorman

Orvik

et al. 2000

Org. Process Res. Dev.

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Two concise syntheses of the experimental rice herbicide 2,2dimethyl-1-(4-methylthio-5-pyrimidinyl)indane are reported. The initial synthesis relies on a low-temperature addition of 5-lithio-4-methylthiopyrimidine to 2,2-dimethyl-1-indanone to construct the pyrimidinylindane system. Process improvements to this route are described and resulted in the preparation of 90 kg of the title compound on pilot plant scale. Economics dictated the need to identify a new synthetic route which utilized inexpensive raw materials. Detailed herein is the initial discovery of a new route which features a novel combination of dissolving metal reduction/formylation/cyclization to construct the requisite pyrimidine ring. Process improvements to this chemistry have allowed us to deliver an appropriately substituted pyrimidinylindane in a minimal number of synthetic operations.

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Section: Resultsmentioning

confidence: 99%