Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides

Boyle, Timothy J.; Guerrero, Fernando; Alam, Todd M.; Dunnigan, Kaylee A.; Sears, Jeremiah M.; Wheeler, David R.

doi:10.1021/acs.inorgchem.9b03134

Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides

Journal Article · Sun Dec 15 23:00:00 EST 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b03134· OSTI ID:1601436

^[1]; Guerrero, Fernando ^[1]; ^[1]; Dunnigan, Kaylee A. ^[1]; Sears, Jeremiah M. ^[1]; Wheeler, David R. ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)

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 (Bu^t-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')(OC₆H_4–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, Bu^t-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-L_x 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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1601436

Report Number(s):: SAND--2019-10594J; 679189

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 1 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides

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