Hydroboration Of Alkenes Research Articles

Cationic Co(I)-Intermediates for Hydrofunctionalization Reactions: Regio- and Enantioselective Cobalt-Catalyzed 1,2-Hydroboration of 1,3-Dienes.

Much of the recent work on catalytic hydroboration of alkenes has focused on simple alkenes and styrene derivatives with few examples of reactions of 1,3-dienes, which have been reported to undergo mostly 1,4-additions to give allylic boronates. We find that reduced cobalt catalysts generated from 1,n- bis-diphenylphosphinoalkane complexes [Ph2P-(CH2) n-PPh2]CoX2; n = 1-5) or from (2-oxazolinyl)phenyldiarylphosphine complexes [(G-PHOX)CoX2] (G = 4-substituent on oxazoline ring) effect selective 1,2-, 1,4-, or 4,3-additions of pinacolborane (HBPin) to a variety of 1,3-dienes depending on the ligands chosen. Conditions have been found to optimize the 1,2-additions. The reactive catalysts can be generated from the cobalt(II)-complexes using trimethylaluminum, methyl aluminoxane, or activated zinc in the presence of sodium tetrakis[(3,5-trifluoromethyl)phenyl]borate (NaBARF). The complex, (dppp)CoCl2, gives the best results (ratio of 1,2- to 1,4-addition >95:5) for a variety of linear terminal 1,3-dienes and 2-substituted 1,3-dienes. The [(PHOX)CoX2] (X = Cl, Br) complexes give mostly 1,4-addition with linear unsubstituted 1,3-dienes, but, surprisingly, selective 1,2-additions with 2-substituted or 2,3-disubstituted 1,3-dienes. Isolated and fully characterized (X-ray crystallography) Co(I)-complexes, (dppp)3Co2Cl2 and [( S,S)-BDPP]3Co2Cl2, do not catalyze the reaction unless activated by a Lewis acid or NaBARF, suggesting a key role for a cationic Co(I) species in the catalytic cycle. Regio- and enantioselective 1,2-hydroborations of 2-substituted 1,3-dienes are best accomplished using a catalyst prepared via activation of a chiral phosphinooxazoline-cobalt(II) complex with zinc and NaBARF. A number of common functional groups, among them, -OBn, -OTBS, -OTs, N-phthalimido- groups, are tolerated, and er's > 95:5 are obtained for several dienes including 1-alkenylcycloalk-1-enes. This operationally simple reaction expands the realm of asymmetric hydroboration to provide direct access to a number of nearly enantiopure homoallylic boronates, which are not readily accessible by current methods. The resulting boronates have been converted into the corresponding alcohols, potassium trifluororoborate salts, N-BOC amines, and aryl derivatives by C-BPin to C-aryl transformation.

Branched-Selective Alkene Hydroboration Catalyzed by Earth-Abundant Metals.

Catalytic hydroboration of alkenes is a well-established method to access borane-functionalized hydrocarbons. While linear-selective hydroboration was predominantly reported, catalysts enabling opposite selectivity (branched-selective) are attracting considerable interest, especially when Earth-abundant metals are utilized. This Synopsis summarizes recent progress in Earth-abundant-metal-catalyzed, branched-selective hydroboration of alkenes while overviewing the historical contributions to this reaction using precious metals. Lessons learned from the current state of this topic that can guide future catalyst design are presented, along with challenging issues that remain to be addressed.

Heterogeneous Additive-Free Hydroboration of Alkenes Using Cu–Ni/Al2O3: Concerted Catalysis Assisted by Acid–Base Properties and Alloying Effects

This study describes our development of a Cu-based heterogeneous catalytic system for additive-free hydroboration of alkenes. Surveying monometallic Cu supported on various oxides revealed that Al2...

Earth-Abundant Metal Catalysis Enabled by Counterion Activation.

A precatalyst activation strategy has been developed for earth-abundant metal catalysis enabled by counterion dissociation and demonstrated through alkene hydroboration. Commercially available iron and cobalt tetrafluoroborate salts were found to catalyze the hydroboration of aryl and alkyl alkenes with good functional group tolerance (Fe, 12 substrates; Co, 13 substrates) with three structurally distinct ligands. Key to this endogenous activation was counterion dissociation to generate fluoride which indirectly activates the precatalyst by reaction with pinacol borane.

Lewis Acid Catalyzed Hydroboration of Alkynes and Alkenes

Key words hydroboration - alkynes - alkenes - scandium catalysis - Lewis acid catalysis

Regioselective radical hydroboration of electron-deficient alkenes: synthesis of α-boryl functionalized molecules.

A regioselective radical hydroboration of various electron-deficient alkenes is achieved by the employment of an NHC-boryl radical. A range of α-borylated nitriles, trifluoromethyl molecules, phosphonates, sulfones, and gem-diboron compounds have been prepared from readily available starting materials. Further synthetic applications of these products are also demonstrated.

Lithium compounds as single site catalysts for hydroboration of alkenes and alkynes.

The hydroboration of alkenes and alkynes using easily accessible lithium compounds [2,6-di-tert-butyl phenolatelithium (1a) and 1,1' dilithioferrocene (1b)] has been achieved with good yields, high functional group tolerance and excellent chemoselectivity. Deuterium-labeling experiments confirm the cis-addition of pinacolborane. The methodology has been further extended to myrcene, which undergoes selective 4,3-hydroboration. DFT calculations provide insights into the mechanism.

NBuLi-promoted anti-Markovnikov selective hydroboration of unactivated alkenes and internal alkynes

A novel anti-Markovnikov selective hydroboration of alkenes and alkynes with HBpin using nBuLi as an effective initiator is described.

Hydroboration of terminal olefins with pinacolborane catalyzed by new 2-iminopyrrolyl iron(ii) complexes

New Fe(ii) mono(2-iminopyrrolyl) complexes catalyze the hydroboration of terminal olefins with pinacolborane via a borane oxidative addition pathway.

Redox switchable catalysis utilizing a fluorescent dye

This report describes the implementation of a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye into the ligand framework of a Rh-based catalyst. The redox-active nature of the BODIPY dye is utilized to generate a catalyst that is capable of exhibiting redox-switchable catalytic behavior for the hydroboration of alkenes through a BODIPY-based reduction.

Aluminium complex-catalysed hydroboration of alkenes and alkynes

Catalytic hydroboration of terminal alkenes/alkynes with HBpin using the Al(III) catalyst, [κ2-{Ph2P(=Se)NCH2(C5H4N)}Al(CH3)2] (1), under mild and solvent-free conditions to afford corresponding alkyl/alkenyl boronate esters in high yield is reported.

A phenalenyl-based nickel catalyst for the hydroboration of olefins under ambient conditions.

In this report, nickel-catalyzed hydroboration of vinylarenes and aliphatic alkenes is investigated. The non-innocent phenalenyl ligand moiety in the nickel complex Ni(PLY)2(THF)2 (1) was utilized as an electron reservoir for the selective hydroboration reaction in the presence of pinacolborane under ambient conditions. The mechanistic investigations revealed that the alkene hydroboration reaction takes place through a single electron transfer (SET) from the phenalenyl ligand backbone leading to the cleavage of the B-H bond.

Alkene hydroboration with pinacolborane catalysed by lithium diisobutyl-tert-butoxyaluminum hydride.

Here we developed a highly efficient alkene hydroboration protocol, showing that various alkyl boronates can be smoothly obtained in good yields by reacting alkenes with pinacolborane (HBpin) in the presence of 5 mol% lithium diisobutyl-tert-butoxyaluminum hydride. The coordination of aluminate ions with lithium cations allowed for effective hydride transfer during hydroboration, and the obtained boronate ester was further used for C–C coupling, trifluoroboronate salt formation, and oxidation to alcohol.

Markovnikov-Selective Hydroboration of Vinylarenes Catalyzed by a Cobalt(II) Coordination Polymer.

Highly efficient and practical hydroboration of alkenes has been catalyzed by an inexpensive and air-stable cobalt(II) coordination polymer (CP) in the presence of KO tBu. Complete conversion of alkenes to alkylboronates were performed within just 5 min with low catalyst loading (0.025 mol %), achieving the record high turnover frequencies of up to 47 520 h-1. For a range of vinylarenes, unusual Markovnikov selectivity was observed.

Room Temperature Iron-Catalyzed Transfer Hydrogenation and Regioselective Deuteration of Carbon-Carbon Double Bonds.

An iron catalyst has been developed for the transfer hydrogenation of carbon-carbon multiplebonds. Using a well-defined β-diketiminate iron(II) precatalyst, a sacrificial amine and a borane, even simple, unactivated alkenes such as 1-hexene undergo hydrogenation within 1 h at room temperature. Tuning the reagent stoichiometry allows for semi- and complete hydrogenation of terminal alkynes. It is also possible to hydrogenate aminoalkenes and aminoalkynes without poisoning the catalyst through competitive amine ligation. Furthermore, by exploiting the separate protic and hydridic nature of the reagents, it is possible to regioselectively prepare monoisotopically labeled products. DFT calculations define a mechanism for the transfer hydrogenation of propene with nBuNH2 and HBpin that involves the initial formation of an iron(II)-hydride active species, 1,2-insertion of propene, and rate-limiting protonolysis of the resultant alkyl by the amine N-H bond. This mechanism is fully consistent with the selective deuteration studies, although the calculations also highlight alkene hydroboration and amine-borane dehydrocoupling as competitive processes. This was resolved by reassessing the nature of the active transfer hydrogenation agent: experimentally, a gel is observed in catalysis, and calculations suggest this can be formulated as an oligomeric species comprising H-bonded amine-borane adducts. Gel formation serves to reduce the effective concentrations of free HBpin and nBuNH2 and so disfavors both hydroboration and dehydrocoupling while allowing alkene migratory insertion (and hence transfer hydrogenation) to dominate.

Copper-catalyzed conjugate addition of in situ formed alkyl boranes to α,β-unsaturated ketones

Conjugate addition of in situ formed organometallic reagents to α,β-unsaturated carbonyl compounds provides an efficient way to generate new C–C bonds. We show optimization of the copper-catalyzed conjugate addition of alkylboranes, which were formed directly in the reaction mixture by hydroboration of alkenes. We have improved the reaction conditions by employing “greener”, less hygroscopic, and higher boiling solvent, 2-methyltetrahydrofuran. We have also broadened the scope of the reaction. Furthermore, chiral ferrocenyl carbene ligands were assessed in the enantioselective version of the transformation with medium enantioselectivity 67:33 e.r.

Biosynthetically Inspired Transformation of Iboga to Monomeric Post-iboga Alkaloids

Summary Organisms have evolved to produce various natural products from a common precursor as a means of maximizing the number of secondary metabolites, thus acquiring selectional advantages. By adopting nature's divergent biosynthetic strategy, we transformed (+)-catharanthine to various iboga and post-iboga alkaloids, including (−)-conodusine A, (+)-conodusines B and C, (−)-voatinggine, (−)-tabertinggine, and (+)-dippinine B. Well-orchestrated oxidations and reorganizations of catharanthine derivatives enabled chemical access to these natural products.

Cobalt-Catalyzed Hydroboration of Alkenes, Aldehydes, and Ketones.

An operationally convenient and general method for hydroboration of alkenes, aldehydes, and ketones employing Co(acac)3 as a precatalyst is reported. The hydroboration of alkenes in the presence of HBpin, PPh3, and NaO tBu affords good to excellent yields with high Markovnikov selectivity with up to 97:3 branched/linear selectivity. Moreover, Co(acac)3 could be used effectively to hydroborate aldehydes and ketones in the absence of additives under mild reaction conditions. Inter- and intramolecular chemoselective reduction of the aldehyde group took place over the ketone functional group.

Palladium-Catalyzed Room Temperature Acylative Cross-Coupling of Activated Amides with Trialkylboranes.

A highly efficient acylative cross-coupling of trialkylboranes with activated amides has been effected at room temperature to give the corresponding alkyl ketones in good to excellent yields by using 1,3-bis(2,6-diisopropyl)phenylimidazolylidene and 3-chloropyridine co-supported palladium chloride, the PEPPSI catalyst, in the presence of K2CO3 in methyl tert-butyl ether. The scope and limitations of the protocol were investigated, showing good tolerance of acyl, cyano, and ester functional groups in the amide counterpart while halo group competed via the classical Suzuki coupling. The trialkylboranes generated in situ by hydroboration of olefins with BH3 or 9-BBN performed similarly to those separately prepared, making this protocol more practical.

Manganese‐Catalyzed Hydrofunctionalization of Alkenes

AbstractThe manganese‐catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields across a variety of sterically and electronically differentiated substrates (25 examples). Alkoxide activation, using NaOtBu, was key to precatalyst activation and reactivity. Catalysis was achieved across various functional groups and on gram‐scale for both the developed methodologies with catalysts loadings as low as 0.5 mol %.