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Volumn 13, Issue 17, 2007, Pages 4805-4815

Computational investigations on the general reaction profile and diastereoselectivity in sulfur ylide promoted aziridination

Author keywords

Aziridination; Density functional calculations; Diastereoselectivity; Reaction mechanisms; Ylides

Indexed keywords

DENSITY FUNCTIONAL THEORY; REACTION KINETICS; SOLVENTS; STEREOSELECTIVITY;

EID: 34250379232     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200700303     Document Type: Article
Times cited : (35)

References (108)
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    • For a review on synthetic transformations with sulfur ylide reactions, see:, Academic Press, New York
    • a) For a review on synthetic transformations with sulfur ylide reactions, see: B. M. Trost, L. S. Melvin, Jr. in Sulfur Ylides - Emerging Synthetic Intermediates, Academic Press, New York, 1975;
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    • For ab initio studies on related ylide mediated reactions, see: a
    • For ab initio studies on related ylide mediated reactions, see: a) F. Volatron, O. Eisenstein, J. Am. Chem. Soc. 1987, 109, 1;
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    • For DFT studies on sulfur ylide mediated epoxidation, see: a
    • For DFT studies on sulfur ylide mediated epoxidation, see: a) V. K. Aggarwal, J. N. Harvey, J. Richardson, J. Am. Chem. Soc. 2002, 124, 5747;
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    • Aggarwal, V.K.1    Harvey, J.N.2    Richardson, J.3
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    • 3CN)/B3LYP/ 6-31G*level.
    • 3CN)/B3LYP/6-31G*level.
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    • See Figure S1 in the Supporting Information for representative structures of In and Out conformers.
    • See Figure S1 in the Supporting Information for representative structures of In and Out conformers.
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    • The relative energies of In and Out conformers for 1-5 are provided in Table S2 in the Supporting Information .
    • The relative energies of In and Out conformers for 1-5 are provided in Table S2 in the Supporting Information .
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    • 16b] They found that the unfavorable interaction between the lone pair on sulfur and phenyl H destabilizes the Out conformer, while the steric interaction between the phenyl group and the methyl hydrogen atoms increases the energy of the In conformer.
    • 16b] They found that the unfavorable interaction between the lone pair on sulfur and phenyl H destabilizes the Out conformer, while the steric interaction between the phenyl group and the methyl hydrogen atoms increases the energy of the In conformer.
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    • In an attempt to sample different conformational possibilities near stationary points such as minima and transition states, we searched the PES along the syn and anti pathways by rotation of the methyl groups attached to the sulfur atom leading to In and Out forms, as stated earlier, Whereas the cisoid pathway resulted in minima/TSs corresponding to both In and Out rotamers of ylides, only one lowest energy geometry was found for the transoid pathway in most cases
    • In an attempt to sample different conformational possibilities near stationary points such as minima and transition states, we searched the PES along the syn and anti pathways by rotation of the methyl groups attached to the sulfur atom (leading to In and Out forms, as stated earlier). Whereas the cisoid pathway resulted in minima/TSs corresponding to both In and Out rotamers of ylides, only one lowest energy geometry was found for the transoid pathway in most cases.
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    • - are on opposite sides: transoid.
    • - are on opposite sides: transoid.
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    • Orientation of Me and R groups is more apparent in the transoid intermediate, after rotation around the newly formed C-C bond.
    • Orientation of Me and R groups is more apparent in the transoid intermediate, after rotation around the newly formed C-C bond.
  • 81
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    • The data in Table 1 correspond to low-energy isomers of TS/intermediates (optimized Cartesian coordinates and energies of different conformers of these intermediates and TSs are provided in the Supporting Information, For elimination TSs, we noticed that the possibilities for bond rotation are quite limited by the requirement of antiperiplanar orientation between the internal nucleophilic nitrogen atom and the leaving group (SMe2, Thus, only those intermediates which are stabilized by weak intramolecular interactions (along with the desired antiperiplanar orientation) can facilitate elimination. Similar restrictions apply to the torsional TSs as well, and therefore only a single TS was found along the anti pathway. However, we could locate additional torsional TSs along the syn pathway for ylides 2, 3, and 5. Unless otherwise specified, the geometries reported in the text pertain to the lowest energy structure obtained through this approach. Relative energies
    • 2). Thus, only those intermediates which are stabilized by weak intramolecular interactions (along with the desired antiperiplanar orientation) can facilitate elimination. Similar restrictions apply to the torsional TSs as well, and therefore only a single TS was found along the anti pathway. However, we could locate additional torsional TSs along the syn pathway for ylides 2, 3, and 5. Unless otherwise specified, the geometries reported in the text pertain to the lowest energy structure obtained through this approach. Relative energies of intermediates and product complexes optimized in the solvent phase and in the gas phase are provided respectively in Tables S3 and S5.
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    • This is in agreement with an earlier report on the addition of ammonium ylides to aldehydes: R. Robiette, M. Conza, V. K. Aggarwal, Org. Biomol. Chem. 2006, 4, 621
    • This is in agreement with an earlier report on the addition of ammonium ylides to aldehydes: R. Robiette, M. Conza, V. K. Aggarwal, Org. Biomol. Chem. 2006, 4, 621.
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    • [17a]
    • [17a]
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    • Corresponding to the In and Out geometries of the ylide, we obtained two cisoid addition TSs each along the anti and syn pathways (the additional cisoid/transoid TSs thus obtained by rotation of SMe2 groups is termed as TS-nc/TS-nt-rotamer in the text, However, in the transoid addition mode, TS search was fruitful only with the In conformer. Thus, a total of six addition TS (C-C bond formation) were identified for 5. Data presented in Table 1 refer only to the lower energy isomers arising from cisoid and transoid modes
    • 2 groups is termed as "TS-nc/TS-nt-rotamer" in the text). However, in the transoid addition mode, TS search was fruitful only with the In conformer. Thus, a total of six addition TS (C-C bond formation) were identified for 5. Data presented in Table 1 refer only to the lower energy isomers arising from cisoid and transoid modes.
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    • However, smaller energy differences predicted between the elimination and addition TSs in the cases of ylides 4 and 5 are reversed with ylide 3. Here, addition TSs are slightly higher in energy and the slowest on the PES (energy profiles for ylides 3 and 4 are provided respectively as Figures S2 and S3 in the Supporting Information).
    • However, smaller energy differences predicted between the elimination and addition TSs in the cases of ylides 4 and 5 are reversed with ylide 3. Here, addition TSs are slightly higher in energy and the slowest on the PES (energy profiles for ylides 3 and 4 are provided respectively as Figures S2 and S3 in the Supporting Information).
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    • See Computational Details for full details of these calculations
    • See Computational Details for full details of these calculations.
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    • 3CN)/B3LYP/6-311G** level on the gas phase (B3LYP/6-31G*) geometries.
    • 3CN)/B3LYP/6-311G** level on the gas phase (B3LYP/6-31G*) geometries.
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    • The gas-phase optimized geometries of selected addition (ylides 2 and 5) and elimination TSs (ylide 5) are provided respectively in Figures S4 and S5 in the Supporting Information. Activation barriers and relative energies of various TSs are summarized in Table S4 in the Supporting Information.
    • The gas-phase optimized geometries of selected addition (ylides 2 and 5) and elimination TSs (ylide 5) are provided respectively in Figures S4 and S5 in the Supporting Information. Activation barriers and relative energies of various TSs are summarized in Table S4 in the Supporting Information.
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    • Gaussian 98 (Revision A. 11.4), M. J. Frisch et al., Gaussian, Inc., Pittsburgh, PA, 2001;
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    • Gaussian03 (RevisionC.02), M. J. Frisch et al., Gaussian, Inc., Wallingford CT, 2004. (See Supporting Information for full citations.)
    • b) Gaussian03 (RevisionC.02), M. J. Frisch et al., Gaussian, Inc., Wallingford CT, 2004. (See Supporting Information for full citations.)


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.