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Title: 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 » intermediate dioxide products of the MPV reduction, which became “trapped” by the Lewis basic solvate.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
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. https://doi.org/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 = {2019},
month = {12}
}

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