Ruthenium(II)-Catalyzed Regioselective Reductive Coupling of α-Imino Esters with Dienes

Zhu, Su‐Li; Lu, Xin; Luo, Yueting; Zhang, Wei; Jiang, Huanfeng; Yan, Ming; Zeng, Wei

doi:10.1021/ol4006079

Cited by 40 publications

(25 citation statements)

References 47 publications

(18 reference statements)

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“…In contrast, the development of corresponding late transition metal catalyzed amine C-H functionalizations has proven challenging. [92][93][94] Indeed, with the exception of the present authors work, [95][96][97][98][99] all other late transition metal catalyzed hydroaminoalkylations require pyridyl directing groups in combination with mono-olefin reactants. [100][101][102][103][104][105][106][107][108] In a significant departure from prior art, it was found that ruthenium catalyzed hydrogen transfer from 4-aminobutanol to 1-substituted-1,3-dienes results in the generation of dihydropyrrole-allylruthenium pairs, which combine to form products of hydroaminoalkylation with good to complete control of anti-diastereoselectivity (Scheme 18).…”

Section: Hydroaminoalkylationmentioning

confidence: 60%

“…In contrast, 2-propanol-mediated reductive couplings of allenes or dienes with formaldimines (generated in situ from saturated 1,3,5-triazines) are efficient and selective processes. [95][96][97][98] Specifically, ruthenium catalyzed transfer hydrogenation of allenes in the presence of 1,3,5-tris(4-methoxyphenyl)-hexahydro-1,3,5-triazine provides products of hydroaminomethylation as single regioisomers. 96 Under similar conditions, butadiene and related 2-substituted dienes engage in regioselective reductive C-C coupling to furnish products of hydroaminomethylation.…”

Section: Hydroaminoalkylationmentioning

confidence: 99%

“…Regioselective 2-propanol mediated reductive coupling of dienes with iminoacetates also have been described (not shown). 98 Whereas ruthenium(II) catalysts promote hydroaminoalkylation through hydrometalative pathways, ruthenium(0) catalysts derived from Ru 3 (CO) 12 and triphos enable catalytic mechanism involving diene-imine oxidative coupling (Scheme 20). 99 Presently, transformations of this type are restricted to the hydroaminoalkylation of isoprene with aryl substituted hydantoins.…”

Section: Hydroaminoalkylationmentioning

confidence: 99%

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Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

Perez

Oda

Geary

et al. 2016

Topics in Current Chemistry Collections

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Section: Hydroaminoalkylationmentioning

confidence: 60%

Section: Hydroaminoalkylationmentioning

confidence: 99%

Section: Hydroaminoalkylationmentioning

confidence: 99%

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Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

Perez

Oda

Geary

et al. 2016

Topics in Current Chemistry Collections

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“…[25] A mixture of ethyl glyoxylate (20.4 mg, 0.20 mmol), substituted amine (0.20 mmol) and anhydrous sodium sulfate (1.0 mmol) in 2 mL of toluene was stirred for 0.5 hour at room temperature. The mixture was then filtered and the solvent was removed under reduced pressure to produce the corresponding a-imino esters.…”

Section: Procedures For the Preparation Of A-imino Estersmentioning

confidence: 99%

“…a-Imino ester (1j) were prepared using the previously reported procedure. [25] All the alkenes substrates are commercially available. These are not the final page numbers!…”

mentioning

confidence: 99%

Copper‐Catalyzed Addition of Alkylboranes to Iminoacetates: Access to α‐Alkyl Branched α‐Amino Acids

Xiao

Zhang

et al. 2016

Adv Synth Catal

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Highly Diastereo‐ and Enantioselective Cu‐Catalyzed Borylative Coupling of 1,3‐Dienes and Aldimines

et al. 2016

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AC u-catalyzed diastereo-and enantioselective borylative coupling reaction of 1,3-dienes with imines was realized. Branched homoallylic amines are readily prepared in as yn-selective manner with high regio-, diastereo-and enantioselectivity.M oreover,t hese three-component coupling reactions feature good functional-group compatibility and easy access to the substrates and catalyst.Asymmetric allylation reactions [1] of imines have received increasing interests from the synthesis community [2] because enantioenriched homoallylic amine products are useful building blocks in organic synthesis and medicinal chemistry.[3] Copper catalysis is an efficient approach to promote the enantioselective addition of terminal allyl transmetalation reagents (e.g., with B, Si, and Sn) to imines, [4] however,C ucatalyzed asymmetric, nucleophilic addition to imines with functionalized (e.g., g-substituted) allyl metal reagents remain challenging.T his is probably due to inefficiencyo f the transmetalation event arising from increased steric hindrance,t he weak electrophilicity/reactivity of imines, and/or difficulties in predicting the regio-and stereochemical outcome of additions.N ew and efficient approaches to generating and utilizing functionalized allyl metal reagents in the presence of acopper catalyst hold promise for accessing complex homoallylic amines,a nd these methods will expand the application of catalytic asymmetric allylation chemistry.Since the seminal work of borylcopper catalysis reported by the Ito [5] and the Miyaura [6] groups,C u-catalyzed borylative coupling reactions have been recognized as an important method for generating boron-containing organocopper species in situ from an unsaturated hydrocarbon. [7] In this context, Hoveyda pioneered the use of boron-functional allylcopper intermediates in enantioselective allylation of aldehydes/ketones, [7f] allyllic esters, [7i] and enoates.[7k] However,Cu-catalyzed borylative coupling of unsaturated hydrocarbon substrates and imines is less developed.[8] Conjugated dienes and especially 1,3-dienes,asacommon feedstock, are ideal nucleophilic allyl metal precursors [9] and readily participate in allylic transformations of carbonyls and imines.[10] We envisioned merging the borylcupration of ac onjugated diene [11] (Scheme 1, step A) and enantioselective imine allyl ation (Scheme 1, step B) in the presence of as uitable chiral copper catalyst. This approach could afford useful homoallylic amines containing an easily derivatizable boron motif.In this method, possible complications include the undesired borylation of imines, [12] poisoning of the metal catalyst by imines or products,a nd difficulty in controlling the regio-(linear vs.b ranched products) [7k,11a] and stereoselectivity (enantio-and/or diastereoselectivity).To test the feasibility of our proposed transformation, we chose acomplex of CuCl and chiral sulfoxide-phophine (SOP, L1)[7j] as acatalyst in preliminary experiments.Inthe presence of isoprene (5 equiv), 1.5 equiv of B 2 (pin) 2 ,a nd NaO...

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Ruthenium(II)-Catalyzed Regioselective Reductive Coupling of α-Imino Esters with Dienes

Cited by 40 publications

References 47 publications

Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

Copper‐Catalyzed Addition of Alkylboranes to Iminoacetates: Access to α‐Alkyl Branched α‐Amino Acids

Highly Diastereo‐ and Enantioselective Cu‐Catalyzed Borylative Coupling of 1,3‐Dienes and Aldimines

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