e.g. Filippa Pettersson or Cancer Res. 75(6) , 1102-12, (2015) or 10.1002/anie.201600521

Photostimulated nucleophilic aromatic substitution for halides with carbon nucleophiles. Preparative and mechanistic aspects

MF Semmelhack, T Bargar

Index: Semmelhack, M. F.; Bargar, Thomas Journal of the American Chemical Society, 1980 , vol. 102, # 26 p. 7765 - 7774

Full Text: HTML

Citation Number: 84

Abstract

Abstract: The photo-SRN1 reaction operates efficiently with enolate anions derived from simple ketones and esters, but 2-lithio-1, 3-dithiane gives low yields. The sluggish and inefficient reaction of dialkyl-substituted ketone and ester enolates is traced to hydrogen atom transfer from the carbon adjacent to the enolate anion to the transient phenyl radical. The first systematic survey of intramolecular coupling of ketone enolate anions shows that ...

5-(6-bromo-1,3-benzodioxol-5-yl)pentan-2-one Structure

5-(6-bromo-1,3-...

~19%

5,7,8,9-Tetrahydrocyclohepta[4,5]benzo[1,2-d][1,3]dioxol-6-on Structure

5,7,8,9-Tetrahy...

5-(benzo[d][1,3]dioxol-5-yl)pentan-2-one Structure

5-(benzo[d][1,3...

1-(6,7-dihydro-5H-cyclopenta[f][1,3]benzodioxol-7-yl)ethanone Structure

1-(6,7-dihydro-...

5-bromo-6-(3-bromopropyl)benzo[d][1,3]dioxole Structure

5-bromo-6-(3-br...

~%

1-(5,6,7,8-tetrahydrobenzo[f][1,3]benzodioxol-5-yl)ethanone Structure

1-(5,6,7,8-tetr...

tert-butyl 2-acetyl-5-(6-bromobenzo[d][1,3]dioxol-5-yl)pentanoate Structure

tert-butyl 2-ac...

~%

1-(5,6,7,8-tetrahydrobenzo[f][1,3]benzodioxol-5-yl)ethanone Structure

1-(5,6,7,8-tetr...

6-(6-bromo-1,3-benzodioxol-5-yl)hexan-2-one Structure

6-(6-bromo-1,3-...

~2%

6-benzo[1,3]dioxol-5-yl-hex-3-en-2-one Structure

6-benzo[1,3]dio...

moskachan B Structure

7,8,9,10-tetrahydrocycloocta[4,5]benzo[1,2-d][1,3]dioxol-6(5H)-one Structure

7,8,9,10-tetrah...

Detail

2-Methyl-2-phenylpropanenitrile Structure

2-Methyl-2-phen...

METHYLLITHIUM Structure

~%

3-methyl-3-phenylbutan-2-one Structure

3-methyl-3-phen...

Pinacolone Structure

Bromobenzene Structure

~98%

3,3-DIMETHYL-1-PHENYL-BUTAN-2-ONE Structure

3,3-DIMETHYL-1-...

3,3-dimethyl-1,1-diphenylbutan-2-one Structure

3,3-dimethyl-1,...

Pinacolone Structure

Bromobenzene Structure

~81%

3,3-DIMETHYL-1-PHENYL-BUTAN-2-ONE Structure

3,3-DIMETHYL-1-...

3,3-dimethyl-1,1-diphenylbutan-2-one Structure

3,3-dimethyl-1,...

Detail

Bromobenzene Structure

<6Li>lithiopinacolonate Structure

<6Li>lithiopina...

~38%

3,3-DIMETHYL-1-PHENYL-BUTAN-2-ONE Structure

3,3-DIMETHYL-1-...

3,3-dimethyl-1,1-diphenylbutan-2-one Structure

3,3-dimethyl-1,...

Detail

4-(benzo[d][1,3]dioxol-5-yl)-3,3-dimethylbutan-2-one Structure

4-(benzo[d][1,3...

~43%

2-(2H3)Methyl(3,3,3-2H3)propanoic acid Structure

2-(2H3)Methyl(3...

4-(benzo[d][1,3]dioxol-5-yl)-3,3-dimethylbutan-2-one Structure

4-(benzo[d][1,3...

~%

4-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethylbutan-2-one Structure

4-(6-iodo-1,3-b...

5-(Chloromethyl)-1,3-benzodioxole Structure

5-(Chloromethyl...

~%

4-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethylbutan-2-one Structure

4-(6-iodo-1,3-b...

3-(benzo[d][1,3]dioxol-5-yl)-2,2-dimethylpropanenitrile Structure

3-(benzo[d][1,3...

~%

4-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethylbutan-2-one Structure

4-(6-iodo-1,3-b...

6-(benzo[d][1,3]dioxol-5-yl)-3,3-dimethylhexan-2-one Structure

6-(benzo[d][1,3...

~%

6-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethylhexan-2-one Structure

6-(6-iodo-1,3-b...

3-(3,4-methylenedioxyphenyl)-1-iodopropane Structure

3-(3,4-methylen...

~%

6-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethylhexan-2-one Structure

6-(6-iodo-1,3-b...

6-(benzo[d][1,3]dioxol-5-yl)-3,3-dimethylhexan-2-one Structure

6-(benzo[d][1,3...

~%

6-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethylhexan-2-one Structure

6-(6-iodo-1,3-b...

Bromobenzene Structure

~%

Benzeneacetic acid, a-methyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

tert-Butyl acetate Structure

tert-Butyl acetate

~%

Benzeneacetic acid, a-methyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

Benzeneacetic acid,1,1-dimethylethyl ester Structure

Benzeneacetic a...

methyl iodide Structure

~%

Benzeneacetic acid, a-methyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

Pinacolone Structure

Bromobenzene Structure

~4%

3,3-DIMETHYL-1-PHENYL-BUTAN-2-ONE Structure

3,3-DIMETHYL-1-...

3,3-dimethyl-1,1-diphenylbutan-2-one Structure

3,3-dimethyl-1,...

Bromobenzene Structure

2,4-dimethyl-3-pentanone Structure

2,4-dimethyl-3-...

~4%

3,3-dimethyl-1,1-diphenylbutan-2-one Structure

3,3-dimethyl-1,...

2,4-Dimethyl-2-phenyl-3-pentanone Structure

2,4-Dimethyl-2-...

Pinacolone Structure

Bromobenzene Structure

~17%

3,3-DIMETHYL-1-PHENYL-BUTAN-2-ONE Structure

3,3-DIMETHYL-1-...

3,3-dimethyl-1,1-diphenylbutan-2-one Structure

3,3-dimethyl-1,...

Detail

Bromobenzene Structure

<6Li>lithiopinacolonate Structure

<6Li>lithiopina...

~12%

3,3-DIMETHYL-1-PHENYL-BUTAN-2-ONE Structure

3,3-DIMETHYL-1-...

3,3-dimethyl-1,1-diphenylbutan-2-one Structure

3,3-dimethyl-1,...

Detail

8-(benzo[d][1,3]dioxol-5-yl)-3,3-dimethyloctan-2-one Structure

8-(benzo[d][1,3...

~%

8-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethyloctan-2-one Structure

8-(6-iodo-1,3-b...

5-(5-iodopentyl)benzo[d][1,3]dioxole Structure

5-(5-iodopentyl...

~%

8-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethyloctan-2-one Structure

8-(6-iodo-1,3-b...

7-(benzo[d][1,3]dioxol-5-yl)-2,2-dimethylheptanenitrile Structure

7-(benzo[d][1,3...

~%

8-(6-iodo-1,3-benzodioxol-5-yl)-3,3-dimethyloctan-2-one Structure

8-(6-iodo-1,3-b...

2-Methyl-2-propanyl 4,4-dimethyl-3-oxopentanoate Structure

2-Methyl-2-prop...

5-bromo-6-(3-bromopropyl)benzo[d][1,3]dioxole Structure

5-bromo-6-(3-br...

~%

7-(6-bromo-1,3-benzodioxol-5-yl)-2,2-dimethylheptan-3-one Structure

7-(6-bromo-1,3-...

4-(6-iodo-1,3-benzodioxol-5-yl)butan-2-one Structure

4-(6-iodo-1,3-b...

~%

3,4-Methylenedioxybenzylacetone Structure

3,4-Methylenedi...

4-Bromoanisole Structure

tert-Butyl acetate Structure

tert-Butyl acetate

~65%

Benzeneacetic acid,1,1-dimethylethyl ester Structure

Benzeneacetic a...

Benzeneacetic acid, a-phenyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

Detail

Bromobenzene Structure

tert-Butyl acetate Structure

tert-Butyl acetate

~77%

Benzeneacetic acid,1,1-dimethylethyl ester Structure

Benzeneacetic a...

Benzeneacetic acid, a-phenyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

4-Bromoanisole Structure

tert-Butyl acetate Structure

tert-Butyl acetate

~29%

Benzeneacetic acid,1,1-dimethylethyl ester Structure

Benzeneacetic a...

Benzeneacetic acid, a-phenyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

Detail

Bromobenzene Structure

tert-Butyl acetate Structure

tert-Butyl acetate

~24%

Benzeneacetic acid,1,1-dimethylethyl ester Structure

Benzeneacetic a...

Benzeneacetic acid, a-phenyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

4-Bromoanisole Structure

tert-butyl 2-methylpropanoate Structure

tert-butyl 2-me...

~5%

Benzeneacetic acid, a,a-dimethyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

Anisole Structure

Bromobenzene Structure

tert-butyl 2-methylpropanoate Structure

tert-butyl 2-me...

~10%

Benzeneacetic acid, a,a-dimethyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

Benzeneacetic acid, a-methyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

methyl iodide Structure

~%

Benzeneacetic acid, a,a-dimethyl-, 1,1-dimethylethyl ester Structure

Benzeneacetic a...

tert-butyl 2-acetyl-5-(6-bromobenzo[d][1,3]dioxol-5-yl)pentanoate Structure

tert-butyl 2-ac...

~%

6-(6-bromo-1,3-benzodioxol-5-yl)hexan-2-one Structure

6-(6-bromo-1,3-...

5-bromo-6-(3-bromopropyl)benzo[d][1,3]dioxole Structure

5-bromo-6-(3-br...

~%

6-(6-bromo-1,3-benzodioxol-5-yl)hexan-2-one Structure

6-(6-bromo-1,3-...