DFT Study on the Sn<sup>II</sup>‐Catalyzed Diastereoselective Synthesis of Tetrahydrofuran from D–A Cyclopropane and Benzaldehyde

Zhang, Jinsheng; Shen, Wei; Li, Ming

doi:10.1002/ejoc.200700216

Cited by 16 publications

(8 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is noted that the ruthenium allenylidene reaction pathway differs from the pathway which has been reported for the Lewis acid catalyzed cycloaddition of aldehydes with donor-acceptor cyclopropanes. [24][25][26][27] We believe that this finding will open up a new aspect of the chemistry of metal allenylidene complexes which can be accessed by a new approach, which differs from known methods using propargylic alcohols and its derivatives. .…”

Section: Methodsmentioning

confidence: 85%

Ruthenium‐Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates

Miyake¹,

Endo²,

Moriyama³

et al. 2013

Angewandte Chemie

View full text Add to dashboard Cite

Transition metal allenylidene complexes have attracted considerable attention as versatile organometallic species for carbon-rich architecture, material science, and reactive intermediates in various organic transformations. [1][2][3] Since the first discovery of metal allenylidene complexes, [4] their structures, electronic properties, and stoichiometric reactivities have been studied extensively owing to the discovery of general method of access to metal allenylidene complexes by simple activation of propargylic alcohols (Scheme 1 a). [5] Although the involvement of transition metal allenylidene complexes in catalytic reactions was reported for the first time in 1992, [6] significant progress has not been made until recently. Since our finding of the ruthenium-catalyzed propargylic substitution reactions of propargylic alcohols with nucleophiles, [7] we have continuously studied a variety of unique catalytic transformations [8][9][10][11] involving ruthenium allenylidene complexes as key and common intermediates together with their enantioselective versions. Furthermore, other research groups have also developed a variety of catalytic reactions involving metal allenylidene complexes as key intermediates. [1,[12][13][14][15] However, readily accessible precursors for formation of allenylidene complexes are limited only to propargylic alcohols and their derivatives. We have now designed an ethynylcyclopropane bearing two carboxy groups at the homopropargylic position as a new accessible precursor for a metal allenylidene complex. The isomerization of a cyclopropyl vinylidene complex can lead to the corresponding metal allenylidene complex, which is expected to serve as a 1,3-dipolar synthon at the g and e positions (Scheme 1 b). In fact, we report herein the ruthenium-catalyzed [3+2] cycloaddition of ethynylcyclopropanes with aldehydes and aldimines, where ruthenium allenylidene complexes serve as reactive intermediates. The scope and limitations of the catalytic [3+2] cycloaddition are described together with the density functional theory (DFT) calculations on the proposed reaction pathway, including the generation of ruthenium allenylidene complexes.Treatment of 1 a with benzaldehyde (2 a; 5 equiv) and BF 3 ·OEt 2 (5 equiv) in the presence of 5 mol % of the methanethiolato-bridged diruthenium complex [{Cp*RuCl-(m 2 -SMe)} 2 ] [9,16] (3 a; Cp* = h 5 -C 5 Me 5 ) in ClCH 2 CH 2 Cl at room temperature for 15 hours afforded dimethyl 5-ethynyl-2-phenyltetrahydrofuran-3,3-dicarboxylate (4 a) in 88 % yield (Table 1, entry 1). The reaction of 1 a with 3 equivalents of 2 a proceeded smoothly, but a lower yield (67 %) of 4 a was observed (Table 1, entry 2). When the amount of BF 3 ·OEt 2 was reduced to 3 equivalents relative to 1 a, the yield of 4 a decreased slightly (Table 1, entry 3). We confirmed that no formation of 4 a was observed in either the absence of BF 3 ·OEt 2 or 3 a, thus indicating that use of both BF 3 ·OEt 2 and 3 a is necessary for producing 4 a. Other diruthenium complexes such as the complex bearing ...

show abstract

Section: Methodsmentioning

confidence: 85%

Ruthenium‐Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates

Miyake¹,

Endo²,

Moriyama³

et al. 2013

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

“…34 This computational method was successfully applied in the mechanistic studies of transition-metal-or non-transition-metal-catalyzed reactions. 23,[35][36][37][38][39][40][41] Frequency calculations at the same level were performed to confirm each stationary point to be either a minimum or a transition structure (T). The transition states were verified by intrinsic reaction coordinate (IRC) 42 calculations and by animating the negative eigenvector coordinates with a visualization program (Molekel 4.3).…”

Section: Computational Detailsmentioning

confidence: 99%

Gold(I)-Catalyzed Cycloaddition of 1-(1-Alkynyl)cyclopropyl Ketones with Nucleophiles To Yield Substituted Furans: A DFT Study

Zhang

Shen

et al. 2009

Organometallics

Self Cite

View full text Add to dashboard Cite

By means of density functional theory (DFT), the mechanism for the synthesis of highly substituted furan (2) from 1-(1-alkynyl)-cyclopropyl ketone (1) with nucleophile (MeOH) catalyzed by Au(I) was investigated. As demonstrated, both the intimate ion-pair [AuL]+ ·[OTf]− (L = PPh3, PMe3, and PH3, OTf = trifluoromethane sulfonate) and the cation [AuL]+ exhibit catalysis, and the former is dominant. Moreover, the bigger the ligand coordinated to gold is, the poorer the catalysis is. The theoretical study reveals that the nucleophiles such as MeOH are important for this reaction, that the reaction between the bicyclo[4.1.0]heptan and the carbinol is a stereospecific addition reaction, and how the proton migration goes through. In the proton migration process, both the anion OTf− and another nucleophile molecule such as MeOH act as a proton shuttle to transport a proton from the nucleophile to the 2-position carbon of alkynyl. The most favorable mechanism includes the activation of the substrate, nucleophile attraction, an addition reaction of the carbonyl triple bond, a stereospecific attack of the nucleophile on the activated cyclopropane, proton migration, and regeneration of the catalyst. The substrate 1 is activated by its combination with Au(I) and a molecule of nucleophile (MeOH), which leads to a decrease in the orbital energy of π*(C1C2) and σ*(C3−C5) and an increase in the dipole moment of the bent bond σ(C3−C5). On the whole, the solvent effects increase the reaction barriers.

show abstract

“…The geometries of all the species were fully optimized by using density functional theory (DFT) of the B3LYP method , with the 6-31G(d,p) basis set for all atoms except for Pt, for which the small-core Los Alamos (LANL2TZ(f)) pseudopotentials and basis sets that include the Dunning–Huzinaga full TZ and Los Alamos ECPs plus TZ have been employed with an extra f polarization function . This computational method was successfully applied in the mechanistic studies of transition-metal- and non-transition-metal-catalyzed reactions. − Vibrational frequency calculations done at the B3LYP/6-31G(d,p) level of theory were used to characterize all of the stationary points as either minima (the number of imaginary frequencies (NIMAG=0) or transition states (NIMAG=1)). The relative energies are thus corrected for the vibrational zero-point energies (ZPE, not scaled).…”

Section: Methodsmentioning

confidence: 99%

DFT Study on the Mechanism of PtCl₂-Catalyzed Rearrangement of Cyclopropenes to Allenes

2012

View full text Add to dashboard Cite

The mechanisms of PtCl 2 -catalyzed rearrangement of cyclopropenes to allenes have been investigated using density functional theory calculations carried out at the B3LYP/6-31G(d,p) (LANL2TZ(f) for Pt) level of theory. The solvent effect was taken into account by B3LYP/6-311++G(d,p) (LANL2TZ(f) for Pt) single-point calculations with the integral equation formalism polarizable continuum model (IEFPCM) in dichloromethane. The radii and nonelectrostatic terms were taken from Truhlar and co-workers' universal solvation model (SMD). Three pathways which lead to the formation of allene via a [1,2]-C−C bond migration (regioselectivity) and C−Si bond migration were performed. Our calculations suggest the following. (1) The major pathway of the cycle involves an initial [1,2]-silyl shift leading to a platinum intermediate. A subsequent [1,2]-C−C bond shift of this intermediate then provides the corresponding allenes. ( 2) Due to the consequence of an interaction between the Lewis acidic platinum and the allene, the rearrangement of α-alkoxy-substituted cyclopropenes does not give the allene as the final product. (3) The calculations suggest that the electronic effect of a silyl substituent on the cyclopropene is essential for this reaction. Furthermore, the silyl groups provide not only the β-cation-stabilizing effect but also a facile migration group for the whole reaction.

show abstract

DFT Study on the Sn^II‐Catalyzed Diastereoselective Synthesis of Tetrahydrofuran from D–A Cyclopropane and Benzaldehyde

Cited by 16 publications

References 30 publications

Ruthenium‐Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates

Ruthenium‐Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates

Gold(I)-Catalyzed Cycloaddition of 1-(1-Alkynyl)cyclopropyl Ketones with Nucleophiles To Yield Substituted Furans: A DFT Study

DFT Study on the Mechanism of PtCl₂-Catalyzed Rearrangement of Cyclopropenes to Allenes

Contact Info

Product

Resources

About

DFT Study on the SnII‐Catalyzed Diastereoselective Synthesis of Tetrahydrofuran from D–A Cyclopropane and Benzaldehyde

Cited by 16 publications

References 30 publications

Ruthenium‐Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates

Ruthenium‐Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates

Gold(I)-Catalyzed Cycloaddition of 1-(1-Alkynyl)cyclopropyl Ketones with Nucleophiles To Yield Substituted Furans: A DFT Study

DFT Study on the Mechanism of PtCl2-Catalyzed Rearrangement of Cyclopropenes to Allenes

Contact Info

Product

Resources

About

DFT Study on the Sn^II‐Catalyzed Diastereoselective Synthesis of Tetrahydrofuran from D–A Cyclopropane and Benzaldehyde

DFT Study on the Mechanism of PtCl₂-Catalyzed Rearrangement of Cyclopropenes to Allenes