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

. alpha.-Amino carbanions via formamidines. Alkylation of pyrrolidines, piperidines, and related heterocycles

AI Meyers, PD Edwards, WF Rieker…

Index: Meyers,A.I.; Edwards,P.D.; Rieker,W.F. Journal of the American Chemical Society, 1984 , vol. 106, p. 3270

Full Text: HTML

Citation Number: 106

Abstract

Abstract: a-Metalation of piperidine, pyrrolidine, hexahydroazepine, 1, 3-thiazolidine, and 1, 3-thiazane has been accomplished via their N-tert-butylformamidine derivatives. Alkylation of these a-amino carbanions via their lithio or cuprate derivatives leads to good yields of a- substituted heterocycles. Similarly, 1, 2, 5, 6-tetrahydropyridine metalates at the 2 position, but alkylates at the 4 position. Reduction leads to 4-substituted piperidines. Evidence is ...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-methylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

2-Propanamine, 2-methyl-N2-[1-tetrahydro-1H-1-pyrrolylmethylidene] Structure

2-Propanamine, ...

methyl iodide Structure

~%

N-tert-butyl-1-(2-methylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-butylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

1-Bromobutane Structure

2-Propanamine, 2-methyl-N2-[1-tetrahydro-1H-1-pyrrolylmethylidene] Structure

2-Propanamine, ...

~%

N-tert-butyl-1-(2-butylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-heptylazepan-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-(2-heptylazepan-1-yl)methanimine Structure

N-tert-butyl-1-...

~82%

2-heptylazepane Structure

2-heptylazepane

tert-Butyl-[1-(4-cyclohexyl-3,4-dihydro-2H-pyridin-1-yl)-meth-(E)-ylidene]-amine Structure

tert-Butyl-[1-(...

~51%

4-Cyclohexylpiperidine Structure

4-Cyclohexylpip...

1-(2-benzylpyrrolidin-1-yl)-N-tert-butylmethanimine Structure

1-(2-benzylpyrr...

~92%

2-Benzylpyrrolidine Structure

2-Benzylpyrrolidine

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-prop-2-enylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

2-Propanamine, 2-methyl-N2-[1-tetrahydro-1H-1-pyrrolylmethylidene] Structure

2-Propanamine, ...

allyl bromide Structure

~%

N-tert-butyl-1-(2-prop-2-enylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-phenylselanylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(4-butyl-3,4-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

1-Bromobutane Structure

N-tert-butyl-1-(3,6-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

~%

N-tert-butyl-1-(4-butyl-3,4-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-(2-prop-2-enylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

~78%

2-(2-propen-1-yl)-Pyrrolidine Structure

2-(2-propen-1-y...

Piperidine,4-(diphenylmethyl)- Structure

Piperidine,4-(d...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~60%

1-(4-benzhydrylpiperidin-1-yl)-N-tert-butylmethanimine Structure

1-(4-benzhydryl...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-methylpiperidin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

methyl iodide Structure

~%

N-tert-butyl-1-(2-methylpiperidin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-(2-propylpiperidin-1-yl)methanimine Structure

N-tert-butyl-1-...

~81%

(±)-Coniine Structure

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-butylpiperidin-1-yl)methanimine Structure

N-tert-butyl-1-...

Butyl iodide Structure

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

~%

N-tert-butyl-1-(2-butylpiperidin-1-yl)methanimine Structure

N-tert-butyl-1-...

1,2,3,6-Tetrahydropyridine Structure

1,2,3,6-Tetrahy...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~76%

N-tert-butyl-1-(3,6-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(6-butyl-3,6-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

1-Bromobutane Structure

N-tert-butyl-1-(3,6-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

~%

N-tert-butyl-1-(6-butyl-3,6-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(3,4-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

~%

N-tert-butyl-1-(3,4-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-[2-(cyclopentylmethyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

1-bromo-5-hexene Structure

1-bromo-5-hexene

~%

N-tert-butyl-1-(3,4-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-[2-(cyclopentylmethyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...

1-(2-benzylpiperidin-1-yl)-N-tert-butylmethanimine Structure

1-(2-benzylpipe...

~85%

2-Benzylpiperidine Structure

2-Benzylpiperidine

N-tert-butyl-1-(2-butylpyrrolidin-1-yl)methanimine Structure

N-tert-butyl-1-...

~71%

2-butylpyrrolidine Structure

2-butylpyrrolidine

Thiazolidine Structure

Formamide,N-(1,1-dimethylethyl)- Structure

Formamide,N-(1,...

~%

N-tert-butyl-1-(1,3-thiazolidin-3-yl)methanimine Structure

N-tert-butyl-1-...

1,3-thiazinane Structure

Formamide,N-(1,1-dimethylethyl)- Structure

Formamide,N-(1,...

~40%

N-tert-butyl-1-(1,3-thiazinan-3-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-[2-(3-chloropropyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

1-Bromo-3-chloropropane Structure

1-Bromo-3-chlor...

~%

N-tert-butyl-1-[2-(3-chloropropyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-(2-propylazepan-1-yl)methanimine Structure

N-tert-butyl-1-...

N,N-dimethyl tert-butylamino-formamidine Structure

N,N-dimethyl te...

~%

N-tert-butyl-1-[2-(cyclopentylmethyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...

(Iodomethyl)cyclopentane Structure

(Iodomethyl)cyc...

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

~%

N-tert-butyl-1-[2-(cyclopentylmethyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

~%

N-tert-butyl-1-(3,4-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-[2-(cyclopentylmethyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-piperidin-1-ylmethanimine Structure

N-tert-butyl-1-...

1-bromo-5-hexene Structure

1-bromo-5-hexene

~%

N-tert-butyl-1-(3,4-dihydro-2H-pyridin-1-yl)methanimine Structure

N-tert-butyl-1-...

N-tert-butyl-1-[2-(cyclopentylmethyl)piperidin-1-yl]methanimine Structure

N-tert-butyl-1-...