159531-47-2

Upstream product

• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 106-95-6 allyl bromide 
• 31729-70-1 bis(iodozinc)methane 
• 7103-09-5 4-but-1-enylmagnesium bromide 
• 75-11-6 diiodomethane 
• 821-41-0 5-Hexen-1-ol 
• 1449-46-3 benzyltriphenylphosphonium bromide 
• 1119-51-3 bromopentene 
• 201852-49-5 potassium (E)-trifluoro(styryl)borate 
• 100-42-5 styrene 

Downstream Products

• 10201-58-8 (E)-1-heptenylbenzene 

Relevant academic research and scientific papers

A highly effective phosphoramidite ligand for asymmetric allylic substitution

Very high enantioselectivity has been achieved both in the copper-catalyzed alkylation of allylic substrates by Grignard and organozinc reagents and in the iridium-catalyzed animation of cinnamyl carbonate by employing a very efficient phosphoramidite ligand (see scheme).

Stepwise Reaction of Bis(iodozincio)methane with Two Different Electrophiles

Keywords: C-C coupling; copper; palladium; zinc

Cobalt-Catalyzed Regioselective Olefin Isomerization under Kinetic Control

Olefin isomerization is a significant transformation in organic synthesis, which provides a convenient synthetic route for internal olefins and remote functionalization processes. The selectivity of an olefin isomerization process is often thermodynamically controlled. Thus, to achieve selectivity under kinetic control is very challenging. Herein, we report a novel cobalt-catalyzed regioselective olefin isomerization reaction. By taking the advantage of fine-tunable NNP-pincer ligand structures, this catalytic system features high kinetic control of regioselectivity. This mild catalytic system enables the isomerization of 1,1-disubstituted olefins bearing a wide range of functional groups in excellent yields and regioselectivity. The synthetic utility of this transformation was highlighted by the highly selective preparation of a key intermediate for the total synthesis of minfiensine. Moreover, a new strategy was developed to realize the selective monoisomerization of 1-alkenes to 2-alkenes dictated by installing substituents on the γ-position of the double bonds. Mechanistic studies supported that the in situ generated Co-H species underwent migratory insertion of double bond/β-H elimination sequence to afford the isomerization product. The less hindered olefin products were always preferred in this cobalt-catalyzed olefin isomerization due to an effective ligand control of the regioselectivity for the β-H elimination step.

Iron-Catalyzed Regioselective Oxo- and Hydroxy-Phthalimidation of Styrenes: Access to α-Hydroxyphthalimide Ketones

This paper describes the aerobic oxidation of styrenes catalyzed by iron(III) chloride (FeCl3) to form β-keto-N-alkoxyphthalimides in fair to good yields. This oxidative process employs mild conditions with green and atom efficient dioxygen (O2) as the oxidant.

Stereospecific Ni-catalyzed cross-coupling of potassium alkenyltrifluoroborates with alkyl halides

A general method for the alkenylation of alkyl electrophiles using nearly stoichiometric amounts of the air- and moisture-stable potassium organotrifluoroborates has been developed. Various functional groups were tolerated on both the nucleophilic and electrophilic partner. Reactions of highly substituted E- and Z-alkenyltrifluoroborates, as well as vinyl- and propenyltrifluoroborates, were successful, and no loss of stereochemistry or regiochemistry was observed.

Cobalt-catalyzed trimethylsilylmethylmagnesium-promoted radical alkenylation of alkyl halides: A complement to the Heck reaction

A cobalt complex, [CoCl2(dpph)] (DPPH = [1,6- bis(diphenylphosphino)hexane]), catalyzes an intermolecular styrylation reaction of alkyl halides in the presence of Me3SiCH2MgCl in ether to yield β-alkylstyrenes. A variety of alkyl halides including alkyl chlorides can participate in the styrylation. A radical mechanism is strongly suggested for the styrylation reaction. The sequential isomerization/styrylation reactions of cyclopropylmethyl bromide and 6-bromo-1-hexene provide evidence of the radical mechanism. Crystallographic and spectroscopic investigations on cobalt complexes reveal that the reaction would begin with single electron transfer from an electron-rich (diphosphine)bis(trimethylsilylmethyl)cobalt(II) complex followed by reductive elimination to yield 1,2-bis(trimethylsilyl)ethane and a (diphosphine)cobalt(I) complex. The combination of [CoCl 2(dppb)] (DPPB = [1,4-bis(diphenylphosphino)butane]) catalyst and Me3SiCH2-MgCl induces intramolecular Heck-type cyclization reactions of 6-halo-1-hexenes via a radical process. On the other hand, the intramolecular cyclization of the prenyl ether of 2-iodophenol would proceed in a fashion similar to the conventional palladium-catalyzed transformation. The nonradical oxidative addition of carbon(sp2)-halogen bonds to cobalt is separately verified by a cobalt-catalyzed cross-coupling reaction of alkenyl halides with Me3SiCH2MgCl with retention of configuration of the starting vinyl halides. The cobalt-catalyzed intermolecular radical styrylation reaction of alkyl halides is applied to stereoselective variants. Styrylations of 1-alkoxy-2-bromocyclopentane derivatives provide trans-1-alkoxy-2-styrylcyclopentane skeletons, one of which is optically pure.

Transition-metal-catalyzed sequential cross-coupling of bis(iodozincio)methane and -ethane with two different organic halides

Bis(iodozincio)methane, prepared from diiodomethane and zinc, reacts with an organic halide in the presence of a transition-metal catalyst to give an iodozinciomethylenated compound; this then reacts with another organic halide to form a C-C bond. The overall process connects two electrophiles with one carbon atom. Bis(iodozincio)ethane can also undergo this transformation, yielding a new stereogenic center. The asymmetric induction of this stereogenic center was investigated by using a chiral palladium catalyst.

Tandem copper-catalyzed enantioselective allylation-metathesis

(matrix presented) Grignard reagents undergo enantioselective (up to 86% ee) copper-catalyzed SN2′ substitution on achiral allylic chlorides. The reaction is wide in scope for both the Grignard reagent and the allylic substrate. The resulting terminal alkene could be submitted to intra-or intermolecular metathesis to afford new chiral synthons. The experimental conditions are compatible with a one-pot overall substitution - metathesis procedure without loss of enantioselectivity.