49748-92-7

Upstream product

• 1674-10-8 1,2-dimethylcyclohexene 
• 2207-01-4 cis-1,2-dimethylcyclohexane 
• 6876-23-9 1,2-trans-dimethylcyclohexane 
• 937-14-4 3-chloro-benzenecarboperoxoic acid 

Relevant academic research and scientific papers

Stereoselective oxidation of alkanes with: M -CPBA as an oxidant and cobalt complex with isoindole-based ligands as catalysts

Two complexes with isoindole-core ligands of general formula [M{C6H4C(NH2)NC(ONCMe2)2}2](NO3)2 (M = Co for 1 and M = Ni for 2) were studied as catalysts for the mild stereoselective alkane oxidation with m-chloroperbenzoic acid (m-CPBA) as an oxidant and cis-1,2-dimethylcyclohexane (cis-1,2-DMCH) as a main model substrate. Complex 1 disclosed a pronounced activity, with high retention of stereoconfiguration of substrates (>98% for cis-1,2-DMCH) and highest cis/trans ratio of tertiary alcohols (products) of 56, under mild conditions. The best achieved yields of tertiary cis-alcohols were of 13.7 and 50.5%, based on the substrate (cis-1,2-DMCH) and the oxidant (m-CPBA) respectively. Kinetic experiments, high bond and stereoselectivity parameters, kinetic isotope effect of 7.2(2) in the oxidation of cyclohexane, and incorporation of 18O from H218O support the involvement of CoIVO high-valent metal-oxo intermediates as main C-H attacking species.

Site-Selective Aliphatic C-H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide

Methods for the practical, intermolecular functionalization of aliphatic C-H bonds remain a paramount goal of organic synthesis. Free radical alkane chlorination is an important industrial process for the production of small molecule chloroalkanes from simple hydrocarbons, yet applications to fine chemical synthesis are rare. Herein, we report a site-selective chlorination of aliphatic C-H bonds using readily available N-chloroamides and apply this transformation to a synthesis of chlorolissoclimide, a potently cytotoxic labdane diterpenoid. These reactions deliver alkyl chlorides in useful chemical yields with substrate as the limiting reagent. Notably, this approach tolerates substrate unsaturation that normally poses major challenges in chemoselective, aliphatic C-H functionalization. The sterically and electronically dictated site selectivities of the C-H chlorination are among the most selective alkane functionalizations known, providing a unique tool for chemical synthesis. The short synthesis of chlorolissoclimide features a high yielding, gram-scale radical C-H chlorination of sclareolide and a three-step/two-pot process for the introduction of the β-hydroxysuccinimide that is salient to all the lissoclimides and haterumaimides. Preliminary assays indicate that chlorolissoclimide and analogues are moderately active against aggressive melanoma and prostate cancer cell lines.

Surface-mediated reactions. 3. Hydrohalogenation of alkenes

Appropriately prepared silica gel and alumina have been found to mediate the addition of HCl, HBr, and HI to alkenes. The technique has been rendered even more convenient by the use of various organic and inorganic halides that undergo hydrolysis in the presence of silica gel or alumina to generate hydrogen halides in situ. Under these conditions alkenes such as cycloheptene (1), 1-octene (7), and 3,3-dimethyl-1-butene (15), which react with HCl only very slowly in solution, underwent rapid addition. 1-Octene (7) underwent ionic addition of HBr without competing radical addition. 1,2-Dimethylcyclohexane (24) afforded the syn addition product 25c, which underwent equilibration with the thermodynamically more stable isomer 25t. A mechanism for surface-mediated addition/elimination is proposed involving a stepwise transfer of H+ and X- from or to the surface in syn fashion, as shown in Scheme II.