Preparation of α-Nitroketones. C-Acylation of Primary Nitroparaffins<sup>1</sup>

Bachman, G. Bryant; Hokama, Takeo

doi:10.1021/ja01527a031

Cited by 36 publications

(5 citation statements)

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“…C-Aminoimidoylation and C-thiocarbamoylation are both relatively unexplored synthetically in contrast to the wide attention given to C-acylation 1a-c and C-imidoylation. 2a-c This reflects the wide availability of both acylating and imidoylating reagents and the lack of reagents for C-aminoimidoylation and C-thiocarbamoylation. Literature examples of compounds that could conceptually have been made by C-aminoimidoylation and C-thiocarbamoylation have generally been accessed by multistep synthesis. 3a-d…”

Section: Introductionmentioning

confidence: 99%

C-Aminoimidoylation and C-Thiocarbamoylation of Esters, Sulfones, and Ketones

et al. 2007

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Section: Introductionmentioning

confidence: 99%

C-Aminoimidoylation and C-Thiocarbamoylation of Esters, Sulfones, and Ketones

et al. 2007

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“…1 und 2 entstehen als Folgeprodukte von 0-Acylierungsreaktionen Acyloxynitrosoverbindungen 1 oder Hydroxamsaurederivate 2 [ 6 ] . C, C-Verknupfungen zu u-Nitroketonen treten hingegen bei den Umsetzungen von Nitronaten rnit a-0x0-carbonsaurenitrilen [7] ein, wobei die Ausbeuten im Falle von Benzoylcyanid 50-70%, rnit aliphatischen Ketonitrilen jedoch nur 30-40% betragen. Weiterhin wurden C-Acylierungen bei der Reaktion von 3 rnit Nitromethan zu 4 [8], bei den Umsetzungen von Nitronaten des Nitromethans mit Phthalsaureanhydrid [9], Benzil [ 101, Acylimidazolen [ 1 la]…”

unclassified

“…-I3C-NMR. (CDC13): 7,38, 10,31 ( 2 q~, 2 CH3); 23,44,33,15 ( 2 q~, 2 CH2); 95,50 (d, C6H11N03 (145,16) Ber. C 49,65 H 7,64 N 9,65% Gef.…”

mentioning

confidence: 99%

Umsetzungen von Dilithio‐nitroalkanen und ‐allylnitroderivaten mit Carbonylverbindungen

Lehr¹,

Gonnermann²,

Seebàch³

1979

Helvetica Chimica Acta

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Reactions of dilithio-nitroalkanes and dilithio-allylnitroalkanes with carbonyl compounds SummaryPrimary nitro compounds can by acylated via dilithium derivatives 5 with carbonic-acid derivatives to give a-nitro esters 6a-i and with carboxylic-acid esters and anhydrides to give a-nitroketones 6j-q. In the reaction of I-nitro-1-buten with two mol-equiv. of butyllithium, the dilithium compound 10 is formed by successive Michael-addition and nitronate deprotonation. Dilithium derivatives 5 also react with ketones and benzaldehyde (4 18a-g); the nitro aldols 25 and 26 are likewise formed by addition of doubly deprotonated allylic nitro compounds. Some of the products have been further transformed by reduction or by Nef-reactions to the hydrochloride of the a-amino-acid 26, to 2-amino-alcohols 28a and 28b, to a-hydroxyamino-acid esters 27a-c, to a-hydroxyimino esters 35 and 36, to a-hydroxyimino ketones 31 and 33, to the a-diketone 34, and to the a-keto ester 37. Schon die friihen Arbeiten von Kissel

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“…Building upon the use of a nitro-acetophenone precursor, it has been previously shown that the analogous nitrile-acetophenone could be cyclized successfully to the quinolone, suggesting a similar strategy from nitro-acetophenone 5 should be viable. We envisioned multiple ways to access the nitro-acetophenone group within 5 , most proceeded via acylation of nitromethane by an activated aryl acyl species such as the acyl benzotriazole (BTA), acyl imidazole (Im), acyl cyanide, or phenoxy ester (OPh) (Figure b). A recently reported one-step method by the group of Skrydstrup operates via palladium catalyzed carbonylative arylation of nitromethane.…”

Section: Introductionmentioning

confidence: 99%

Exploration of a Nitromethane-Carbonylation Strategy during Route Design of an Atropisomeric KRAS^G12C Inhibitor

et al. 2021

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Route design and proof of concept synthesis was conducted on a synthetically challenging atropisomeric KRASG12C inhibitor to support clinical API manufacture. Improvements to the synthesis of a chiral piperazine fragment gave reduced step count and streamlined protecting group strategy via the formation and methanol ring opening of an N-carboxy-anhydride (NCA). The complex atropisomeric nitroquinoline was accessed via an early stage salt-resolution followed by a formal two-part nitromethane-carbonylation, avoiding a high temperature Gould–Jacobs cyclization that previously led to atropisomer racemization. The substrate scope of the formal nitromethane-carbonylation strategy was further explored for a range of ortho-substituted bromo/iodo unprotected anilines.

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Preparation of α-Nitroketones. C-Acylation of Primary Nitroparaffins¹

Cited by 36 publications

References 1 publication

C-Aminoimidoylation and C-Thiocarbamoylation of Esters, Sulfones, and Ketones

C-Aminoimidoylation and C-Thiocarbamoylation of Esters, Sulfones, and Ketones

Umsetzungen von Dilithio‐nitroalkanen und ‐allylnitroderivaten mit Carbonylverbindungen

Exploration of a Nitromethane-Carbonylation Strategy during Route Design of an Atropisomeric KRAS^G12C Inhibitor

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Preparation of α-Nitroketones. C-Acylation of Primary Nitroparaffins1

Cited by 36 publications

References 1 publication

C-Aminoimidoylation and C-Thiocarbamoylation of Esters, Sulfones, and Ketones

C-Aminoimidoylation and C-Thiocarbamoylation of Esters, Sulfones, and Ketones

Umsetzungen von Dilithio‐nitroalkanen und ‐allylnitroderivaten mit Carbonylverbindungen

Exploration of a Nitromethane-Carbonylation Strategy during Route Design of an Atropisomeric KRASG12C Inhibitor

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Preparation of α-Nitroketones. C-Acylation of Primary Nitroparaffins¹

Exploration of a Nitromethane-Carbonylation Strategy during Route Design of an Atropisomeric KRAS^G12C Inhibitor