Synthesis, regioselective deprotonation, and stereoselective alkylation of fluoro ketimines

Welch, John T.; Seper, Karl W.

doi:10.1021/jo00248a017

Cited by 81 publications

(25 citation statements)

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“…Previously, it has been shown that fluorinated imines can undergo a manifold of reactions that are difficult to access with fluorinated aldehydes or ketones [37–40]. While there are many reports of the utility of trifluoroacetaldimines [41–44], there is only a single report of the preparation of N- ethyl 3,3,3-trifluoropropanaldimine [45], the trifluoromethyl analog of pentafluorosulfanylacetaldehyde ( 1a ).…”

Section: Resultsmentioning

confidence: 99%

Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines

Penger¹,

Hahmann²,

Filatov³

et al. 2013

Beilstein J. Org. Chem.

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Summaryβ-Lactams were diastereoselectively formed by the reaction of SF5-containing aldimines, or an SF5-containing ketimine, with benzyloxyketene in a conrotatory ring closure process. Imine formation and cyclization were possible in spite of the acidification of protons on the carbon bound to SF5. The reactions of the aldimines demonstrated very good 1,2-lk diastereoselectivity, however lack of stereochemical control of the C–N ketimine geometry was reflected in the stereochemistry of the product β-lactam. Cyclization of imines with a stereogenic center bearing SF5 was reflected in the 1,2-lk,lk selectivity of the β-lactam.

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Section: Resultsmentioning

confidence: 99%

Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines

Penger¹,

Hahmann²,

Filatov³

et al. 2013

Beilstein J. Org. Chem.

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“…The absolute configuration of the major enantiomers was inferred from the sign of their circular dichroism spectra identical to those observed for the compounds in entries 10 and 11, [10] whose stereochemistry was determined by comparison of their optical rotation with that of the known compounds. [6] [d] The reaction was carried out with [Pd 2 (dba) 3 ] (5 mol %) and 6 (12.5 mol %).…”

Section: Methodsmentioning

confidence: 99%

“…Keywords: allylation · asymmetric synthesis · decarboxylation · enantioselectivity · fluoroketones [c] The enantiomeric excess was determined by chiral HPLC analysis, except in entries 7 and 11 for which it was determined by GC analysis (see Supporting Information). The absolute configuration of the major enantiomers was inferred from the sign of their circular dichroism spectra identical to those observed for the compounds in entries 10 and 11, [10] whose stereochemistry was determined by comparison of their optical rotation with that of the known compounds. [6] [d] The reaction was carried out with [Pd 2 (dba) 3 ] (5 mol %) and 6 (12.5 mol %).…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of Chiral α‐Fluoroketones through Catalytic Enantioselective Decarboxylation

et al. 2005

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Ein innovatives Konzept liefert die optisch aktiven α‐Fluorketone 3 in hohen Ausbeuten und mit bis zu 99 % ee ausgehend von racemischen α‐Fluor‐β‐ketoestern 1 in Gegenwart des chiralen Phosphanyloxazolin‐Liganden 2. Durch diese palladiumkatalysierte Decarboxylierung/Allylierung können überdies ausschließlich kohlenstoffsubstituierte quartäre Stereozentren hoch enantioselektiv aufgebaut werden. dba=Dibenzylidenaceton.

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“…The reports include alkylations [3], reactions with aldehydes, and ketones [4]. In one case of fluorinated species, temperature-dependent regioselective alkylations to α-fluoroimines could be achieved [5].…”

Section: Introductionmentioning

confidence: 99%

Use of 3‐Halo‐1‐azaallylic Anions in Heterocyclic Chemistry

2004

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Abstract:The synthetic potential of lithio 3-halo-1-azaallylic anions as building blocks in organic chemistry and especially in heterocyclic chemistry will be highlighted by the synthesis of functionalized imines, obtained after reaction of 3-halo-1-azaallylic anions with heteroatom-substituted electrophiles. Thus, the latter generated functionalized imines are suitable building blocks for the synthesis of a whole range of heterocycles and physiologically active compounds, including agrochemicals and pharmaceuticals. 3-Halo-1-azaallylic anions were used in the synthesis of N-alkyl-3,3-dichloroazetidines, 2,3-disubstituted pyrroles, piperidines, 2-substituted pyridines, 2-alkoxytetrahydrofurans, etc., from which a large range of useful and interesting chemicals can be produced, e.g., 2-azetines and 9-alkyl-2-phenyl-3aβ, 4,6,7,8,9,9aβ,9bβ-octahydro-1H-pyrrolo[3,4,h]quinoline-1,3-diones. The utility of the present methodology is demonstrated by the synthesis of the pheromone (S)-manicone, the sulfur-containing flavor compound 2-[(methylthio)methyl]-2-butenal, and some agrochemical and pharmaceutical compounds.

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Synthesis, regioselective deprotonation, and stereoselective alkylation of fluoro ketimines

Cited by 81 publications

References 0 publications

Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines

Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines

Synthesis of Chiral α‐Fluoroketones through Catalytic Enantioselective Decarboxylation

Use of 3‐Halo‐1‐azaallylic Anions in Heterocyclic Chemistry

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