Hydrogen/Deuterium Exchange Reactions of Olefins with Deuterium Oxide Mediated by the Carbonylchlorohydrido‐ tris(triphenylphosphine)ruthenium(II) Complex

Tse, Sunny Kai San; Xue, Peng; Lin, Zhenyang; Jia, Guochen

doi:10.1002/adsc.201000037

Cited by 66 publications

(55 citation statements)

References 140 publications

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“…It should be noted that protons from the reactant alcohol or adventitious water may contribute to diminished levels of deuterium incorporation. 22 …”

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confidence: 99%

Enantioselective Ruthenium-Catalyzed Carbonyl Allylation via Alkyne–Alcohol C–C Bond-Forming Transfer Hydrogenation: Allene Hydrometalation vs Oxidative Coupling

et al. 2015

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“…It should be noted that protons from the reactant alcohol or adventitious water may contribute to diminished levels of deuterium incorporation. 22 …”

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confidence: 99%

Enantioselective Ruthenium-Catalyzed Carbonyl Allylation via Alkyne–Alcohol C–C Bond-Forming Transfer Hydrogenation: Allene Hydrometalation vs Oxidative Coupling

et al. 2015

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“…This pattern of deuterium incorporation suggests allene hydrometallation is fast and reversible and occurs with incomplete regioselectivity.I ncomplete deuterium incorporation at the interior vinylic position of deuterio-3a (71 % 2 H) likely stems from b-hydride elimination of the allylruthenium species to form dienes,w hich are detected in crude reaction mixtures and may account for the requirement of as uperstoichiometric amount of allene.A dventitious water also may diminish the extent of deuterium incorporation. [24] Thecoupling of 1a to the deuterated triazine deuterio-2a delivers deuterio-3a, which completely retains deuterium adjacent to nitrogen (> 95 % 2 H), thus indicating that the CÀNb ond of the amine product is not subject to reversible dehydrogenation under these reaction conditions. In summary,w er eport an ew strategy for the hydroaminomethylation of p-unsaturated reactants beyond classical hydroformylation/reductive amination:t he reductive coupling of allenes and N-aryl formaldimines by rutheniumcatalyzed transfer hydrogenation.…”

Section: Angewandte Zuschriftenmentioning

confidence: 98%

Hydroaminomethylation Beyond Carbonylation: Allene–Imine Reductive Coupling by Ruthenium‐Catalyzed Transfer Hydrogenation

2015

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Ruthenium(II)-catalyzed hydrogen transfer from 2-propanol mediates reductive coupling of 1,1-disubstituted allenes with formaldimines with complete branch-regioselectivity,t hus representing an ew method for hydroaminomethylation beyond classical hydroformylation/reductive amination. Hydroaminomethylation,[1] thes uccessive one-pot hydroformylation/reductive amination, is an important, atomefficient method for amine synthesis [Scheme 1, Eq. (1)].Subsequent to Reppes discovery of hydroaminomethylation at BASF in 1949, [2] relatively few studies were disclosed.[3]However,inthe last 15 years,due in large part to the elegant work of Eilbracht, [4] hydroaminomethylation has been intensively investigated [1] and utilized for the preparation of diverse pharmaceutical ingredients, [5] including cinacalcet (Sensipar, Mimpara), [5,6a] ibutilide (Corvert), [5, 6b] and fexofenadine (Allegra, Fexidine,T elfast, Fastofen, Tilfur,V ifas, Te lfexo,A llerfexo). [5,6c] Recent advances in hydroaminomethylation include the use of ammonia as ar eactant, [4c,7] regioselective reactions of terminal [8a] and internal [8b alkenes through ligand control [8] or the use of directing groups, [9] the evolution from rhodium-based to ruthenium-based catalysts, [10] and the emergence of noncarbonylative strategies, including hydroaminoalkylation [11] [Scheme 1, Eq. (2)] and photoredox catalysis [Scheme 1, Eq. (3)].[12] Thevast majority of hydroaminomethylation protocols apply to a-olefins.T o our knowledge,t he hydroaminomethylation of other punsaturated reactants,s uch as dienes or allenes,i s unknown.[13] Herein we report an ew strategy for hydroaminomethylation based on 2-propanol-mediated reductive coupling of 1,1-disubstituted allenes and formaldimines derived in situ from 1,3,5-tris(aryl)-hexahydro-1,3,5-triazines [Scheme 1, Eq. (4)].T hese processes deliver branched products of hydroaminomethylation bearing all-carbon quaternary centers. [13][14][15][16][17][18][19][20] Initial experiments were inspired by our earlier studies on the ruthenium-catalyzed reductive coupling of formaldehyde with allenes, [13,14] dienes, [13,15] and alkynes. [13,16] Using the allene 1a and hexahydro-1,3,5-triazine 2a,acrystalline solid prepared from paraformaldehyde and p-anisidine, [21] as eries of catalysts derived from the commercial ruthenium complex [HClRu(CO)(PPh 3 ) 3 ]w ere evaluated for their ability to induce reductive coupling by 2-propanol-mediated transfer hydrogenation (Table 1). In the absence of an exogenous ligand or upon use of tricyclohexylphosphine as al igand, small quantities of the desired homoallylic neopentyl amine 3a were formed as asingle regioisomer.Chelating phosphine ligands were more effective at enforcing higher conversion. Eventually,i tw as found that upon use of dCype as al igand, the desired homoallylic amine 3a could be obtained in 83 % yield.Under optimized reaction conditions using the ruthenium catalyst derived in situ from [HClRu(CO)(PPh 3 ) 3 ]and dCype, the scope of the allene partner was explored in...

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“…The relatively low levels of deuterium incorporation may be attributed to exchange with adventitious water or with the hydroxylic proton deuterio - 1k . 21 …”

Section: Mechanismmentioning

confidence: 99%

Osmium(0)-Catalyzed C–C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation

et al. 2016

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Osmium(0) complexes derived from Os3(CO)12 and XPhos (2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl) catalyze the C-C coupling of α-hydroxy esters 1a-1i, α-ketols 1j-1o or 1,2-diols dihydro-1j-1o with ethylene 2a to form ethylated tertiary alcohols 3a-3o. As illustrated in couplings of 1-octene 2b with vicinally dioxygenated reactants 1a, 1b, 1i, 1j, 1k, 1m, higher α-olefins are converted to adducts 4a, 4b, 4i, 4j, 4k, 4m with complete levels of branched regioselectivity. Oxidation level independent C-C coupling is demonstrated by the reaction of 1-octene 2b with diol dihydro-1k, α-ketol 1k and dione dehydro-1k. Functionalized olefins 2c-2f react with ethyl mandelate 1a to furnish adducts 5a-8a as single regioisomers. The collective data, including deuterium labeling studies, are consistent with a catalytic mechanism involving olefin-dione oxidative coupling to form an oxa-osmacyclopentane, which upon reductive cleavage via hydrogen transfer from the secondary alcohol reactant releases the product of carbinol C-alkylation with regeneration of the ketone. Single crystal X-ray diffraction data of the dinuclear complex Os2(CO)4(O2CR)2(XPhos)2 and the trinuclear complex Os3(CO)11(XPhos) are reported. These studies suggest increased π-backbonding at the stage of the metal-olefin π-complex plays a critical role in facilitating alkene-carbonyl oxidative coupling, as isostructural ruthenium(0) complexes, which are weaker π-donors, do not catalyze the transformations reported herein.

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Hydrogen/Deuterium Exchange Reactions of Olefins with Deuterium Oxide Mediated by the Carbonylchlorohydrido‐ tris(triphenylphosphine)ruthenium(II) Complex

Abstract: The catalytic properties of several ruthenium, osmium and rhodium hydride complexes for hydrogen/deuterium (H/D) exchange between olefins and deuterium oxide (D 2 O) were investigated. The most effective catalytic precursor was found to be the carbonylchlorohydridotris(triphenylphosphine)-

Cited by 66 publications

References 140 publications

Enantioselective Ruthenium-Catalyzed Carbonyl Allylation via Alkyne–Alcohol C–C Bond-Forming Transfer Hydrogenation: Allene Hydrometalation vs Oxidative Coupling

Enantioselective Ruthenium-Catalyzed Carbonyl Allylation via Alkyne–Alcohol C–C Bond-Forming Transfer Hydrogenation: Allene Hydrometalation vs Oxidative Coupling

Hydroaminomethylation Beyond Carbonylation: Allene–Imine Reductive Coupling by Ruthenium‐Catalyzed Transfer Hydrogenation

Osmium(0)-Catalyzed C–C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation

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