Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides
Abstract
A series of titanium alkoxides ([Ti(OR)4] (OR = OCH(CH3)2 (OPri), OC(CH3)3 (OBut), and OCH2C(CH3)3 (ONep)) were modified with a set of substituted hydroxyl-benzaldehydes [HO-BzA-Lx: x = 1, 2-hydroxybenzaldehyde (L = H), 2-hydroxy-3-methoxybenzaldehyde (OMe-3), 5-bromo-2-hydroxybenzaldehyde (Br-5), 2-hydroxy-5-nitrobenzaldehyde (NO2-5); x = 2, 3,5-di-tert-butyl-2-hydroxybenzaldehyde (But-3,5), 2-hydroxy-3,5-diiodobenzaldehyde (I-3,5)] in pyridine (py). Instead of the expected simple substitution, each of the HO-BzA-Lx modifiers were reduced to their respective diol [(py)(OR)2Ti(κ2(O,μ-O')(OC6H4–x(CH2O)-2)(L)x] (OR = OPri, x = 1, L = H (1a), OMe-3 (2a), Br-5 (3a·py), NO2-5 (4a·4py); x = 2, But-3,5 (5a), I-3,5 (6a), ONep; x = 1, L = H (1b), OMe-3 (2b), Br-5 (3b·py), NO2-5 (4b); x = 2, But-3,5 (5b), I-3,5 (6b·py)), as identified by single crystal X-ray studies. The 1H NMR spectral data were complex at room temperature but simplified at high temperatures (70 °C). Diffusion ordered spectroscopy (DOSY) NMR experiments indicated that 2a maintained the dinuclear structure in a solution independent of the temperature, whereas 2b appears to be monomeric over the same temperature range. On the basis of additional NMR studies, the mechanism of the reduction of the HO-BzA-Lx to the dioxide ligand was thought to occur by a Meerwein–Pondorf–Verley (MPV) mechanism. The structures of 1a–6b appear to be themore »
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1601436
- Report Number(s):
- SAND-2019-10594J
Journal ID: ISSN 0020-1669; 679189
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 1; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Redox reactions; X-raysPyridines; Crystal structure; Fourier transform infrared spectroscopy
Citation Formats
Boyle, Timothy J., Guerrero, Fernando, Alam, Todd M., Dunnigan, Kaylee A., Sears, Jeremiah M., and Wheeler, David R. Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.9b03134.
Boyle, Timothy J., Guerrero, Fernando, Alam, Todd M., Dunnigan, Kaylee A., Sears, Jeremiah M., & Wheeler, David R. Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides. United States. https://doi.org/10.1021/acs.inorgchem.9b03134
Boyle, Timothy J., Guerrero, Fernando, Alam, Todd M., Dunnigan, Kaylee A., Sears, Jeremiah M., and Wheeler, David R. Mon .
"Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides". United States. https://doi.org/10.1021/acs.inorgchem.9b03134. https://www.osti.gov/servlets/purl/1601436.
@article{osti_1601436,
title = {Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides},
author = {Boyle, Timothy J. and Guerrero, Fernando and Alam, Todd M. and Dunnigan, Kaylee A. and Sears, Jeremiah M. and Wheeler, David R.},
abstractNote = {A series of titanium alkoxides ([Ti(OR)4] (OR = OCH(CH3)2 (OPri), OC(CH3)3 (OBut), and OCH2C(CH3)3 (ONep)) were modified with a set of substituted hydroxyl-benzaldehydes [HO-BzA-Lx: x = 1, 2-hydroxybenzaldehyde (L = H), 2-hydroxy-3-methoxybenzaldehyde (OMe-3), 5-bromo-2-hydroxybenzaldehyde (Br-5), 2-hydroxy-5-nitrobenzaldehyde (NO2-5); x = 2, 3,5-di-tert-butyl-2-hydroxybenzaldehyde (But-3,5), 2-hydroxy-3,5-diiodobenzaldehyde (I-3,5)] in pyridine (py). Instead of the expected simple substitution, each of the HO-BzA-Lx modifiers were reduced to their respective diol [(py)(OR)2Ti(κ2(O,μ-O')(OC6H4–x(CH2O)-2)(L)x] (OR = OPri, x = 1, L = H (1a), OMe-3 (2a), Br-5 (3a·py), NO2-5 (4a·4py); x = 2, But-3,5 (5a), I-3,5 (6a), ONep; x = 1, L = H (1b), OMe-3 (2b), Br-5 (3b·py), NO2-5 (4b); x = 2, But-3,5 (5b), I-3,5 (6b·py)), as identified by single crystal X-ray studies. The 1H NMR spectral data were complex at room temperature but simplified at high temperatures (70 °C). Diffusion ordered spectroscopy (DOSY) NMR experiments indicated that 2a maintained the dinuclear structure in a solution independent of the temperature, whereas 2b appears to be monomeric over the same temperature range. On the basis of additional NMR studies, the mechanism of the reduction of the HO-BzA-Lx to the dioxide ligand was thought to occur by a Meerwein–Pondorf–Verley (MPV) mechanism. The structures of 1a–6b appear to be the intermediate dioxide products of the MPV reduction, which became “trapped” by the Lewis basic solvate.},
doi = {10.1021/acs.inorgchem.9b03134},
journal = {Inorganic Chemistry},
number = 1,
volume = 59,
place = {United States},
year = {Mon Dec 16 00:00:00 EST 2019},
month = {Mon Dec 16 00:00:00 EST 2019}
}
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