35664-99-4

Upstream product

• 32730-85-1 cycloheptanecarbonitrile 
• 60433-00-3 methyl cycloheptanecarboxylate 
• 7362-77-8 C₁₀H₁₈O₂ 
• 35664-87-0 1-Methylcycloheptacarbonitrile 
• 82322-89-2 ethyl 1-methyl-2-oxocycloheptanecarboxylate ethylene thioketal 
• 82322-90-5 ethyl 1-methyl-cycloheptanecarboxylate 
• 20043-64-5 (2-Methylcycloheptan-1-on-2-yl)-carbonsaeureethylester 
• 35664-93-8 1-methyl-cycloheptanecarboxylic acid 

Downstream Products

• 1534433-45-8 1-(4-methoxybenzyl)-N-(quinolin-8-yl)cycloheptanecarboxamide 
• 1534433-46-9 1-(4-methoxybenzyl)-2-(4-methoxyphenyl)-N-(quinolin-8-yl)cycloheptanecarboxamide 

Relevant academic research and scientific papers

Nickel-Catalyzed Aminoxylation of Inert Aliphatic C(sp3)-H Bonds with Stable Nitroxyl Radicals under Air: One-Pot Route to α-Formyl Acid Derivatives

Nickel-catalyzed aminoxylation of an unactivated C(sp3)-H bond with a stable nitroxyl radical has been accomplished for the first time to offer various N-alkoxyamine derivatives, which further enables a one-pot approach to α-formyl acid derivatives. The aminoxylation process reported also provides direct evidence for the oxidative addition of a cyclometallic intermediate with a free radical, which is helpful for the reaction-mechanism study in transition-metal-catalyzed functionalization of inert C(sp3)-H bonds.

A C-H Insertion Approach to Functionalized Cyclopentenones

Cyclopentenones are synthetically versatile structures, and their straightforward construction from alkynone substrates by employing synthetically streamlining C-H insertion is conceptually appealing and of high synthetic potential. But, its implementation is very limited. Herein we report a Au-catalyzed version, which affords 2-bromocyclopent-2-en-1-ones with a broad scope and synthetically desirable diastereoselectivities. The proposed key intermediate capable of the observed insertion into unactivated C-H bonds is a fully functionalized gold vinylidene, which is generated via a novel intermolecular strategy. This flexible access of likely gold vinylidenes opens various opportunities to explore their versatile reactivities.

Palladium(0)/PAr3-catalyzed intermolecular amination of C(sp3)-H bonds: Synthesis of β-amino acids

An intermolecular C(sp3)-H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2N-OBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3)-H bond by the generated Pd-NR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)-catalyzed C-H arylation reactions. The electron-deficient triarylphosphine ligand is crucial for this C(sp3)-H amination reaction to occur.

Nickel-catalyzed direct arylation of C(sp3)-H bonds in aliphatic amides via bidentate-chelation assistance

The Ni-catalyzed, direct arylation of C(sp3)-H (methyl and methylene) bonds in aliphatic amides containing an 8-aminoquinoline moiety as a bidentate directing group with aryl halides is described. Deuterium-labeling experiments indicate that the C-H bond cleavage step is fast and reversible. Various nickel complexes including both Ni(II) and Ni(0) show a high catalytic activity. The results of a series of mechanistic experiments indicate that the catalytic reaction does not proceed through a Ni(0)/Ni(II) catalytic cycle, but probably through a Ni(II)/Ni(IV) catalytic cycle.

Nickel-catalyzed site-selective alkylation of unactivated C(sp 3)-H bonds

The direct alkylation of unactivated sp3 C-H bonds of aliphatic amides was achieved via nickel catalysis with the assist of a bidentate directing group. The reaction favors the C-H bonds of methyl groups over the methylene C-H bonds and tolerates various functional groups. Moreover, this reaction shows a predominant preference for sp3 C-H bonds of methyl groups via a five-membered ring intermediate over the sp2 C-H bonds of arenes in the cyclometalation step.

Copper-catalyzed site-selective intramolecular amidation of unactivated C(sp3)-H bonds

The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp3 C-H bond functionalization process. The reaction favors predominantly the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds. Moreover, a preference for activating sp3 C-H bonds of β-methyl groups, via a five-membered ring intermediate, over the aromatic sp2 C-H bonds was also observed in the cyclometalation step. Additionally, sp3 C-H bonds of unactivated secondary sp3 C-H bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms. Getting ahead on tams: The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp 3 C-H bond functionalization process to deliver β-lactams. The reaction favors the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds, as well as aromatic C(sp2)-H bonds and unactivated secondary C(sp3)-H bonds of rings.

CATALYTICS ASYMMETRIC ACTIVATION OF UNACTIVATED C-H BONDS, AND COMPOUNDS RELATED THERETO

One aspect of the present invention is directed in part to catalytic and stereoselective functionalization of unactivated C-H bonds of simple organic substrates. The compounds and methods provided herein allow one to control the stereochemistry in a C-H activation step, activate substrates containing α-hydrogens next to the directing group, and remove a directing group under mild conditions. One aspect of the present invention relates to a transition-metal-catalyzed method for selective and asymmetric oxidation of carbons located in a β- or γ-position relative to an auxiliary. Another aspect of the invention relates to the enantiomerically-enriched substrates and the enantiomerically-enriched products formed via said method. In certain embodiments, oxazoline and oxazinone directing groups are used. In addition, the Boc protecting group has been identified as a directing group which does not necessitate removal.

Palladium-catalyzed asymmetric iodination of unactivated C-H bonds under mild conditions

(Chemical Equation Presented) Specific, asymmetric, and mild: Oxazoline (Oxa), a removable chelating chiral auxiliary, assists in the asymmetric activation of C(sp3)-H bonds at the β position and C(sp 2)-H bonds at the γ position. Pd-(OAc)2 is an effective catalyst for the selective and asymmetric iodination of methyl, cyclopropyl, and aryl groups at room temperature (see formulae).

Cyclopentanone Synthesis by Intramolecular Carbon-Hydrogen Insertion of Diazo Ketones. A Diterpene-to-Steroid Skeleton Conversion

Intramolecular carbon-hydrogen insertion on cupric sulfate assisted decomposition of diazomethyl ketones derived from four 1-methylcycloalkanecarboxylic acids and (hexahydrophenyl)acetic, homopivalic, and enanthic acids is shown to yield mostly cyclopentanones.The yields are appreciable in the conformationally favorable cases, and insertion in the solvent cyclohexane can be avoided by the use of Freon TF as the solvent.The conversion of a primaradienic diterpene into a 14-iso-16-androstanone derivative shows the power of the new method of cyclopentanone synthesis.