Geometric Isotope Effect of Various Intermolecular and Intramolecular C−H···O Hydrogen Bonds, Using the Multicomponent Molecular Orbital Method

Udagawa, Taro; Ishimoto, Takayoshi; Tokiwa, Hiroaki; Tachikawa, Masanori; Nagashima, Umpei

doi:10.1021/jp0615656

Cited by 53 publications

(48 citation statements)

References 33 publications

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“…Thus, many-body effect plays a very important role for the equilibrium geometry of porphine molecule, as well as porphycene molecule. 17,18 Our MCគMO method has been already extended to Møller-Plesset perturbation 19 and configuration interaction 20 methods beyond the mean field approximation. Many theoretical methods are developed for the quantum effect of hydrogen nucleus.…”

Section: Introductionmentioning

confidence: 99%

H ∕ D isotope effect on porphine and porphycene molecules with multicomponent hybrid density functional theory

Udagawa

Tachikawa

2006

The Journal of Chemical Physics

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To analyze the H/D isotope effect on porphine and porphycene molecules including the protonic/deuteronic quantum nature and electron correlation efficiently, the authors have developed the new scheme of the multicomponent hybrid density functional theory [MC_(HF+DFT)]. The optimized geometries of porphine, porphycene, and these deuterated isotopomers by our MC_(HF+DFT) method are in good agreement with the experimental "high-symmetric" structures, contrary to the "low-symmetric" geometries optimized by pure multicomponent Hartree-Fock method. The optimized geometries for HD-porphine and HD-porphycene molecules, in which an inner hydrogen is replaced to a deuterium, are found to be low symmetric. Such drastic geometrical change induces the electronic polarization, and gives rise to the slight dipole moment values in these HD species. Their results clearly indicate that the difference of the nuclear quantum nature between inner proton and inner deuteron directly influences the molecular geometry and electronic structure.

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Section: Introductionmentioning

confidence: 99%

H ∕ D isotope effect on porphine and porphycene molecules with multicomponent hybrid density functional theory

Udagawa

Tachikawa

2006

The Journal of Chemical Physics

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“…In the CH 2 @CH 2 ÁH 2 O system, our calculations predict a contraction of 0.4 mÅ of the hydrogenbonded CH group. At the MP2/6-31+G(d,p) [24] or MP2/6-31+G(d) [20] levels, a small contraction of the CH bond has been predicted and at the MP2/6-31++G(d,p) level, an elongation of 0.4 mÅ [25] has been calculated. No variation of the CH distance Table 1 Binding energies (kJ mol À1 ) including ZPE-and BSSE-corrections (in parentheses) for the linear and cyclic structures of the complexes between CH 2 @CHX and water.…”

Section: Variation Of the Ch Distances Vibrational Frequencies And Amentioning

confidence: 98%

“…It is known that in these systems, the geometric changes induced by hydrogen bond formation are very small [17,24]. The geometric isotope effect of the ethylene-water complex has been recently analyzed by using the multicomponent molecular orbital method [25].…”

Section: Introductionmentioning

confidence: 99%

“…Our study includes the optimization of the geometries, the calculation of the binding energies and the harmonic m(CH) stretching vibration along with a natural bond orbital analysis including the charges on the different atoms, the occupation of the antibonding orbitals and the hyperconjugation energies. It must be mentioned that the interaction between ethylene and water has been investigated theoretically [17,24,25], but up to now, only the geometry and binding energy have been reported. The effect of the interaction with water on the non-bonded CH groups has not been discussed in previous works.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical study of the interaction between monohalogenated ethylenes and water

Nguyen

Diep

Zeegers‐Huyskens

2009

Journal of Molecular Structure: THEOCHEM

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“…of 96:4 that was observed for 4 under the same experimental conditions. It is known that CÀD···O bonding is slightly weaker than CÀ H···O bonding in comparison, [17] hence this small decrease of the observed d.r. is likely due to an isotopic effect, which confirms the existence of an H-bonding interaction involving the p-allyl/Pd moiety.…”

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confidence: 90%

Counteranion‐Directed Catalysis in the Tsuji–Trost Reaction: Stereocontrolled Access to 2,5‐Disubstituted 3‐Hydroxy‐Tetrahydrofurans

et al. 2012

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The concept of counteranion-directed catalysis (CDC) is applicable to reactions in which cationic intermediates are formed. [1] In principal, it can even be applied to transitionmetal-catalyzed reactions, [2] as demonstrated for gold catalysis by Toste and co-workers, [3] and for palladium catalysis by List and co-workers. [4] The latter group showed that the positively charged p-allyl/Pd II complex of the Tsuji-Trost reaction [5,6] can interact with a chiral counteranion, thus allowing an efficient direct a allylation of aldehydes by asymmetric counteranion-directed catalysis (ACDC). In the proposed mechanism, the chiral phosphate counteranion establishes hydrogen bonds with the HN moiety of the intermediate enamine as well as an ionic interaction with the charged Pd II center, thus resulting in a very organized transition state (Scheme 1).Herein, we disclose a highly diastereoselective synthesis of 2,5-disubstituted 3-hydroxy-tetrahydrofurans through the formation of a p-allyl/Pd II intermediate, in which the carbox-ylate counterion plays a prominent directing role. We propose a mechanism that is based on DFT calculations and chemical experiments, and which indicates that the stereocontrol may in part be a result of the formation of an unusual noncovalent bond between the counteranion and one of the hydrogen atoms of the cationic p-allyl/Pd complex itself. The two hydroxy groups are also involved in the mechanism, and the sum of all these noncovalent interactions leads preferentially to the highly organized chiral transition state [pR]°(see Schemes 1 and 3), a prediction that accounts well for the observed diastereoselectivity.In the course of our total synthesis of (+)-oocydin A (1; Figure 1), [7] we devised this convenient approach to 2,5disubstituted 3-hydroxy-tetrahydrofuran 4 from the readily available syn diol 3, giving 4 in a surprisingly high d.r. (trans/ cis = 96:4; Scheme 2). This high selectivity was unexpected, considering the work of Hara et al., [8] who observed a poor diastereoselectivity (trans/cis = 37:63) for the cyclization of 5 to 6 (Scheme 2). This result led us to suspect a directing effect of the b-OH group in the stereoselective cyclization of 3 to 4, and prompted us to further explore this promising reaction. The first confirmation of our hypothesis was the observation that even anti diol 7 cyclized diastereoselectively, leading to 2,5-disubstituted 3-hydroxy-tetrahydrofuran 8 [9] (anti/syn = 95:5, 97 % yield; Scheme 2). We must emphasize that in anti diols as well as in syn diols, the newly formed vinyl function is selectively installed trans to the b-OH group (which does not cyclize), while the stereogenic center that bears the g-OH group (which cyclizes) seems to have no impact on the stereoselectivity, which is counterintuitive.In order to gain some insight into the mechanism of this reaction, DFT calculations were carried out, starting with the syn diol series (Scheme 3). [10,11] The nucleophilic attack of the g-OH group at the p-allyl moiety was modeled (outer-sphere mechanism). [...

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Geometric Isotope Effect of Various Intermolecular and Intramolecular C−H···O Hydrogen Bonds, Using the Multicomponent Molecular Orbital Method

Cited by 53 publications

References 33 publications

H ∕ D isotope effect on porphine and porphycene molecules with multicomponent hybrid density functional theory

H ∕ D isotope effect on porphine and porphycene molecules with multicomponent hybrid density functional theory

Theoretical study of the interaction between monohalogenated ethylenes and water

Counteranion‐Directed Catalysis in the Tsuji–Trost Reaction: Stereocontrolled Access to 2,5‐Disubstituted 3‐Hydroxy‐Tetrahydrofurans

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