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

Competing radical, carbanion, and carbene pathways in the reactions of hindered primary alkyl halides with lithium dialkylamides

…, B Park, GS Patil, K Gadru, R Gurumurthy

Index: Ashby, E. C.; Park, B.; Patil, G. S.; Gadru, K.; Gurumurthy, R. Journal of Organic Chemistry, 1993 , vol. 58, p. 424 - 437

Full Text: HTML

Citation Number: 31

Abstract

A variety of methods were utilized to study the mechanism of reaction of 6-iodo-5, 5-dimethyl- 1-hexene and its bromo, chloro, and tosylate derivatives with LDA and several other lithium dialkylamides. In the reaction of 6-iodo-5, 5-dimethyl-l-hexene with LDA in THF, radical, carbanion, and carbene pathways occurred simultaneously. However, when the corresponding bromide was allowed to react with LDA, the radical pathway was minor and ...

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

Detail

2,2-Dimethyl-5-hexenoic acid ethyl ester Structure

2,2-Dimethyl-5-...

~%

6-bromo-5,5-dimethylhex-1-ene Structure

6-bromo-5,5-dim...

2,2-Dimethyl-5-hexen-1-ol Structure

2,2-Dimethyl-5-...

~80%

2,2-dimethylhex-5-enal Structure

2,2-dimethylhex...

6-bromo-5,5-dimethylhex-1-ene Structure

6-bromo-5,5-dim...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-bromo-5,5-dimethylhex-1-ene Structure

6-bromo-5,5-dim...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

1-chloro-2,2-dimethyl-5-hexene Structure

1-chloro-2,2-di...

~%

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

N/A Structure

Detail

2,2-Dimethyl-5-hexenoic acid ethyl ester Structure

2,2-Dimethyl-5-...

~%

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

2,2-Dimethyl-5-hexen-1-ol Structure

2,2-Dimethyl-5-...

~%

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

2,2-Dimethyl-5-hexen-1-ol Structure

2,2-Dimethyl-5-...

Tosyl chloride Structure

~61%

2,2-dimethylhex-5-en-1-ol,4-methylbenzenesulfonic acid Structure

2,2-dimethylhex...

2,2-Dimethyl-5-hexenoic acid ethyl ester Structure

2,2-Dimethyl-5-...

~%

2,2-dimethylhex-5-en-1-ol,4-methylbenzenesulfonic acid Structure

2,2-dimethylhex...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

5,5-Dimethyl-,(Z)-2-Hexene Structure

5,5-Dimethyl-,(...

trans-5,5-dimethyl-2-hexene Structure

trans-5,5-dimet...

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

6-bromo-5,5-dimethylhex-1-ene Structure

6-bromo-5,5-dim...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-bromo-5,5-dimethylhex-1-ene Structure

6-bromo-5,5-dim...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

1-(3-Butenyl)-1-methylcyclopropane Structure

1-(3-Butenyl)-1...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-ethenyl-1,1-dimethylcyclobutane Structure

3-ethenyl-1,1-d...

1,1-dimethyl-2-(2-propenyl)cyclopropane Structure

1,1-dimethyl-2-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~60%

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

1-(3-Butenyl)-1-methylcyclopropane Structure

1-(3-Butenyl)-1...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

Detail

2,2-Dimethyl-5-hexenoic acid ethyl ester Structure

2,2-Dimethyl-5-...

~%

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

2,2-Dimethyl-5-hexen-1-ol Structure

2,2-Dimethyl-5-...

~%

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

2,2-Dimethyl-5-hexen-1-ol Structure

2,2-Dimethyl-5-...

~94%

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

Detail

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1,3-Trimethylcyclopentane Structure

1,1,3-Trimethyl...

1-(3-Butenyl)-1-methylcyclopropane Structure

1-(3-Butenyl)-1...

3-(iodomethyl)-1,1-dimethylcyclopentane Structure

3-(iodomethyl)-...

Detail

2,2-Dimethyl-5-hexenoic acid ethyl ester Structure

2,2-Dimethyl-5-...

~%

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

2,2-Dimethyl-5-hexen-1-ol Structure

2,2-Dimethyl-5-...

~%

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

6-iodo-5,5-dimethylhex-1-ene Structure

6-iodo-5,5-dime...

~%

1,1-dimethyl-3-methylidenecyclopentane Structure

1,1-dimethyl-3-...

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