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Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

ABSTRACT: We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. Study of its reactivity showed that isopropoxy(phenyl)silane is an exceptionally efficient stoichiometric reductant, and it is now possible to significantly decrease catalyst loadings, lower reaction temperatures, broaden functional group tolerance, and use diverse, aprotic solvents in iron- and manganese-catalyzed hydrofunctionalizations. As representative examples, we have improved the yields and rates of alkene reduction, hydration, hydroamination, and conjugate addition. Discovery of this broadly applicable, chemoselective, and solvent-versatile reagent should allow an easier interface with existing radical reactions. Finally, isotope-labeling experiments rule out the alternative hypothesis of hydrogen atom transfer from a redox-active ?-diketonate ligand in the HAT step. Instead, initial HAT from a metal hydride to directly generate a carbon-centered radical appears to be the most reasonable hypothesis.

SUBMITTER: Obradors C

PROVIDER: S-EPMC4858193 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature

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Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

Obradors Carla C Martinez Ruben M RM Shenvi Ryan A RA

Journal of the American Chemical Society 20160330 14

We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. St ...[more]

PMID: 26984323

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Project description:Reported herein are thermochemical studies of hydrogen atom transfer (HAT) reactions involving transition metal H-atom donors M(II)LH and oxyl radicals. [Fe(II)(H(2)bip)(3)](2+), [Fe(II)(H(2)bim)(3)](2+), [Co(II)(H(2)bim)(3)](2+), and Ru(II)(acac)(2)(py-imH) [H(2)bip = 2,2'-bi-1,4,5,6-tetrahydropyrimidine, H(2)bim = 2,2'-bi-imidazoline, acac = 2,4-pentandionato, py-imH = 2-(2'-pyridyl)imidazole)] each react with TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) or (t)Bu(3)PhO(*) (2,4,6-tri-tert-butylphenoxyl) to give the deprotonated, oxidized metal complex M(III)L and TEMPOH or (t)Bu(3)PhOH. Solution equilibrium measurements for the reaction of [Co(II)(H(2)bim)(3)](2+) with TEMPO show a large, negative ground-state entropy for hydrogen atom transfer, -41 +/- 2 cal mol(-1) K(-1). This is even more negative than the DeltaS(o)(HAT) = -30 +/- 2 cal mol(-1) K(-1) for the two iron complexes and the DeltaS(o)(HAT) for Ru(II)(acac)(2)(py-imH) + TEMPO, 4.9 +/- 1.1 cal mol(-1) K(-1), as reported earlier. Calorimetric measurements quantitatively confirm the enthalpy of reaction for [Fe(II)(H(2)bip)(3)](2+) + TEMPO, thus also confirming DeltaS(o)(HAT). Calorimetry on TEMPOH + (t)Bu(3)PhO(*) gives DeltaH(o)(HAT) = -11.2 +/- 0.5 kcal mol(-1) which matches the enthalpy predicted from the difference in literature solution BDEs. A brief evaluation of the literature thermochemistry of TEMPOH and (t)Bu(3)PhOH supports the common assumption that DeltaS(o)(HAT) approximately 0 for HAT reactions of organic and small gas-phase molecules. However, this assumption does not hold for transition metal based HAT reactions. The trend in magnitude of |DeltaS(o)(HAT)| for reactions with TEMPO, Ru(II)(acac)(2)(py-imH) << [Fe(II)(H(2)bip)(3)](2+) = [Fe(II)(H(2)bim)(3)](2+) < [Co(II)(H(2)bim)(3)](2+), is surprisingly well predicted by the trends for electron transfer half-reaction entropies, DeltaS(o)(ET), in aprotic solvents. This is because both DeltaS(o)(ET) and DeltaS(o)(HAT) have substantial contributions from vibrational entropy, which varies significantly with the metal center involved. The close connection between DeltaS(o)(HAT) and DeltaS(o)(ET) provides an important link between these two fields and provides a starting point from which to predict which HAT systems will have important ground-state entropy effects.

Dataset Information

Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

Publications

Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

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