87161-58-8

Upstream product

• 134052-28-1 2-((1S,2R,5S)-2-Isopropyl-5-methyl-cyclohexyloxy)-tetrahydro-pyran 
• 2216-52-6 Neomenthol 
• 15356-70-4 menthol 
• 89-78-1 1R,2RS,4S-(-)-menthol 
• 61548-81-0 (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl methanesulfonate 
• 2216-51-5 (-)-menthol 
• 89-78-1 (-)-menthol 

Downstream Products

• 1441778-34-2 ((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)diphenylphosphine sulfide 
• 1441778-39-7 ((1S,2S,5R)-2-isopropyl-5-methylcyclohexyl)diphenylphosphine sulfide 
• 1441778-25-1 ((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)(methyl)sulfane 

Relevant academic research and scientific papers

Regioselective Hydroalkylation of Vinylarenes by Cooperative Cu and Ni Catalysis

Disclosed here is a dual copper and nickel catalytic system with a silyl hydride source for promoting the linear selective hydroalkylation of vinylarenes. This carbon–carbon bond-forming protocol is applied to couple a variety of functionalized vinylarenes with alkyl halides applying a nickel(II) NNN pincer complex in the presence of an NHC-ligated copper catalyst. This combination allows for a 1 mol % loading of the nickel catalyst leading to turnover numbers of up to 72. Over 40 examples are presented, including applications for pharmaceutical diversification. Labeling experiments demonstrated the regioselectivity of the reaction and revealed that the copper catalyst plays a crucial role in enhancing the rate for formation of the reactive linear alkyl nickel complex. Overall, the presented work provides a complimentary approach for hydroalkylation reactions, whilst providing a preliminary mechanistic understanding of the cooperativity between the copper and nickel complexes.

A mild method for the replacement of a hydroxyl group by halogen: 2. unified procedure and stereochemical studies

N,N-Dimethyl- and N,N-diisopropyl-1-halo-2-methyl-l-propenylamines are readily available reagents for the mild deoxyhalogenation of alcohols and hydroxyacids. In this study we showed that the reactivity of the reagents can be tuned by varying the size of the alkyl groups on the reagents: the replacement of methyl by isopropyl groups led to a significant increase of reactivity. We then described a unified procedure for all deoxyhalogenations using the readily available α-chloroenamines as reagents with (bromination, iodination) or without (chlorination) an alkaline bromide or iodide. Finally, we showed that deoxyhalogenation reactions of secondary alcohols were highly stereospecific and generally occurred with inversion of configuration.

A mild and highly chemoselective iodination of alcohol using polymer supported DMAP

The synthesis of organic compounds using polymer supported catalysts and reagents, where the required product is always in solution, has been of great interest in recent years, both in industries and academia especially in pharmaceutical research. Here, a simple and efficient method for conversion of alcohols into their iodides in high yield using polymer supported 4-(Dimethylamino)pyridine (DMAP) is described. Polymer supported DMAP is used in catalytic amount and is recovered and reused several times. Additionally, this method is highly chemoselective. [Figure not available: see fulltext.]

Iron(III)-catalyzed halogenations by substitution of sulfonate esters

A novel halogenation reaction from sulfonates catalyzed by iron(III) is described. The reaction can be performed as a stoichiometric or a catalytic version. This reaction provides a convenient strategy for the efficient access to structurally diverse secondary chlorides, bromides and iodides. The stereochemical course of the reaction is governed by the substrate and the experimental conditions. Secondary alcohols modified as quisylates or pysylates are substantially more reactive. Aliphatic quisylates proceed with overall inversion of configuration under catalytic conditions. Chemoselectivity in bismesylates was observed in favour of the secondary mesylate. Additionally, based on the experimental results, a possible catalytic cycle for the halogenation has been proposed.

Alkylation of acylmetalates with alkyl halides to prepare Fischer carbene complexes: An improved protocol

Alkoxy Fischer carbene complexes have been synthesized by alkylation of lithium acylmetalates with alkyl halides in the presence of catalytic amount (5-10 mol %) of n-tetrabutylammonium bromide (n-Bu4NBr) restricting the temperature below 55 °C to minimize decomposition of the product. The reaction occurs in a biphasic condition involving water and alkyl halide. The effect of cesium on this alkylation reaction has been studied. The presence of a radical quencher, di-tert-butyl phenol, neither affects the yield nor leads to the formation of dimer of di-tert-butyl phenol, which rules out the possibility of radical pathway mechanism. The kinetic study and the 1H NMR spectra of products suggest an SN2 pathway particularly involving alkyl halides.

Triphenylphosphine/2,3-dichloro-5,6-dicyanobenzoquinone as a new, selective and neutral system for the facile conversion of alcohols, thiols and selenols to alkyl halides in the presence of halide ions

A mixture of triphenylphosphine (Ph3P) and 2,3-dichloro-5,6-dicyanobenzoquinone in CH2Cl2 affords a complex which in the presence of R4NX (X=Cl, Br, I) converts alcohols, thiols and selenols into their corresponding alkyl halides in high yields at room temperature. The method is highly selective for the conversion of 1° alcohols in the presence of 2° ones and also 1° and 2° alcohols in the presence of 3° alcohols, thiols, epoxides, trimethylsilyl- and tetrahydropyranyl ethers, 1,3 dithianes, disulfides, and amides.

A facile conversion of tetrahydropyranyl ethers to the corresponding bromides and iodides

Tetrahydropyranyl ethers are converted to the corresponding bromides and iodides upon reaction with NaI (or Libr) and BF3.Et2O (or ClSiMe3).

Facile Conversion of Primary and Secondary Alcohols to Alkyl Iodides

A convenient, simple procedure is described for the conversion of a variety of primary and secondary alcohols to iodides in yields ranging from 60-98percent.The method employs the Ph3P/imidazole/I2 combination of reagents in the solvent dichloromethane.

SYNTHESIS OF ALKYL HALIDES UNDER NEUTRAL CONDITIONS

Primary and secondary alcohols are efficiently converted to the corresponding alkyl halides under neutral conditions.

NUCLEOPHILIC INVERSIONS OF A CHIRAL ALCOHOL MEDIATED BY ZINC SALTS

In a model study, various zinc salts are shown to behave as efficient nucleophilic reagents in mild conditions for unequivocal inversion of (-) menthol to (+) neomethyl derivatives.