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Synthesis of (saturated) alcohols

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Ionic liquids enhanced the nucleophilicity of water and reduced the formation of elimination products in the nucleophilic hydroxylation of alkyl halides. The reactivity of other nucleophiles such as alcohols, phenol, and acetic acid in an ionic liquid was also investigated.
D. W. Kim, D. J. Hong, J. W. Seo, H. S. Kim, H. K. Kim, C. E. Song, D. Y. Chi, J. Org. Chem., 2004, 69, 3186-3189.

Nucleophilic Hydroxylation in Water Media Promoted by a Hexa-Ethylene Glycol-Bridged Dicationic Ionic Liquid
V. H. Jadhav, J. G. Kim, H. J. Jeong, D. W. Kim, J. Org. Chem., 2015, 80, 7275-7280.

Convenient methods for the preparation of stable and non-volatile mono- and dichloroborane adducts of dioxane from dioxane-BCl₃ and NaBH₄ in the presence of catalytic amounts of tri- or tetraglyme were developed. The dioxane-monochloroborane adduct hydroborates representative olefins cleanly and rapidly and lead to the corresponding alcohols in quantitative yields after oxidation.
J. V. B. Kanth, H. C. Brown, J. Org. Chem, 2001, 66, 5359-5365.

In a remote hydro-oxygenation of alkenes under palladium catalysis, both terminal and internal alkenes are suitable to yield the corresponding linear alcohols efficiently. A compatible SelectFluor/silane redox system plays an essential role for the excellent chemo- and regioselectivities. The reaction features a broad substrate scope and excellent functional group compatibility.
X. Li, X. Yang, P. Chen, G. Liu, J. Am. Chem. Soc., 2022, 144, 22877-22883.

The use of Oxone allows the conversion of various aryl-, heteroaryl-, alkenyl-, and alkyltrifluoroborates into the corresponding oxidized products in excellent yields. This method tolerates a broad range of functional groups, and in secondary alkyl substrates it was demonstrated to be completely stereospecific.
G. A. Molander, L. N. Cavalcanti, J. Org. Chem., 2011, 76, 623-630.

A visible light-induced photocatalysis enables a general and practical decarboxylative hydroxylation of a broad range of carboxylic acids using molecular oxygen as the green oxidant. NaBH₄ as additive reduces unstable peroxyl radical intermediates in situ.
S. N. Khan, M. K. Zaman, R. Li, Z. Sun, J. Org. Chem., 2020, 85, 5019-5026.

A neighboring boronate group in vicinal bis(boronic esters) provides a dramatic rate acceleration in transmetalation to copper and thereby enables unprecedented site-selective cross-couplings allyl, alkynyl, and propargyl electrophiles as well as a simple proton. This cross-coupling operates under practical experimental conditions.
N. Xu, Z. Kong, J. Z. Wang, G. J. Lovinger, J. P. Morken, J. Am. Chem. Soc., 2022, 144, 17815-17823.

The combination of sBuLi and TMEDA in CPME at -60 °C enables deprotonation of unactivated, chiral secondary dialkyl TIB esters. These carbanions were reacted with a range of neopentyl boronic esters which, after 1,2-metalate rearrangement and oxidation, gave a range of tertiary alcohols in high yield and high ee. Further functional group transformations of the tertiary boronic esters were demonstrated.
A. P. Pulis, D. J. Blair, E. Torres, V. K. Aggarwal, J. Am. Chem. Soc., 2013, 135, 16054-16057.

In a Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand, a (EtO)₂MeSiH/BQ redox system is vital for the highly selective and efficient hydrooxygenation. This method provides efficient access to a broad range of optically pure alcohol esters from easily available alkenes with excellent enantioselectivities.
X. Yang, X. Li, P. Chen, G. Liu, J. Am. Chem. Soc., 2022, 144, 7972-7977.

Using commercially available Ph₃PAuCl and readily prepared, benign arylsilanes, a gold-catalyzed oxyarylation of alkenes proceeds smoothly in air. The oxidant, Selectfluor, not only facilitates entry to the Au(I/III) manifold but also provides a fluoride anion for silane activation, thereby avoiding the need for addition of a stoichiometric base.
L. T. Ball, M. Green G. C. Lloyd-Jones, C. A. Russel, Org. Lett., 2010, 12, 4724-4727.

An air-stable half-sandwich ruthenium complex is a highly active catalyst for the anti-Markovnikov reductive hydration of alkynes, involving the decarboxylation of formic acid, hydration of the alkyne, and hydrogenation of the intermediate aldehyde. A wide array of terminal alkynes are efficiently processed to linear alcohols using as little as 2 mol % of catalyst at ambient temperature.
M. Zeng, L. Li, S. B. Herzon, J. Am. Chem. Soc., 2014, 136, 7058-7067.

Two complementary dual catalytic systems enable a highly regioselective reductive hydration of terminal alkynes to yield branched or linear alcohols in very good yield. The method is compatible with terminal, di-, and trisubstituted alkenes. This reductive hydration constitutes a strategic surrogate to alkene oxyfunctionalization and may be of utility in multistep settings.
L. Li, S. B. Herzon, J. Am. Chem. Soc., 2012, 134, 17376-17378.

L. Li, S. B. Herzon, J. Am. Chem. Soc., 2012, 134, 17376-17378.

(Hydrido)silyl ethers, generated in situ by dehydrogenative coupling of tertiary alcohols with diethylsilane, undergo regioselective silylation at a primary C-H bond δ to the hydroxyl group in the presence of [(Xantphos)Rh(Cl)] as catalyst. Fleming-Tamao oxidation of the resulting 6-membered oxasilolanes provides 1,4-diols.
C. Karmel, B. Li, J. F. Hartwig, J. Am. Chem. Soc., 2018, 140, 1460-1470.

(NH₄)₂S₂O₈ mediates a metal-free three-component alkene oxyalkynylation using H₂O or alcohol as oxygenation agent. The reversed regioselectivity should be dictated by an alkene radical cation intermediate.
Y. Li, R. Lu, S. Sun, L. Liu, Org. Lett., 2018, 20, 6836-6839.

The use of N-oxides in butanol as solvent enables a site-selective oxidation of vicinal bis(boronates) with good efficiency and selectivity across a range of substrates to provide 2-hydro-1-boronic esters, which are shown to be versatile intermediates in the synthesis of chiral building blocks.
L. Yan, J. P. Morken, Org. Lett., 2019, 21, 3760-3763.

An NH₄I-promoted and H₂O-controlled intermolecular difunctionalization of alkenes provides bis-methylsulfanes and β-hydroxysulfides via methylthiyl radical addition to the double bond to give a carbon-centered radical, which immediately cyclizes to a thiiranium ion, followed by combination with H₂O to afford β-hydroxysulfides. In the absence of water, 1,2-disulfenylation takes place.
R. He, X. Chen, Y. Li, Q. Liu, C. Liao, L. Chen, Y. Huang, J. Org. Chem., 2019, 84, 8750-8758.

Related

The cyclopropenone catalyzed nucleophilic substitution of alcohols by methanesulfonate ion with inversion of configuration provides an alternative to the Mitsunobu reaction. The new reaction avoids the use of azodicarboxylates and generation of hydrazine and phosphine oxide byproducts and is compatible with a range of functionality.
E. D. Nacsa, T. H. Lambert, Org. Lett., 2013, 15, 38-41.

By careful selection of appropriate enzymes (alcohol dehydrogenases [ADH] and cofactor recycling enzymes), cofactor recycling of NADH can be performed in the presence of NADP⁺ recycling to achieve overall (R)- or (S)-selective deracemisations of sec-alcohols or stereoinversion representing a possible concept for a “green” equivalent to the chemical-intensive Mitsunobu inversion.
C. V. Voss, C. C. Gruber, K. Faber, T. Knaus, P. Macheroux, W. Kroutil, J. Am. Chem. Soc., 2008, 130, 13969-13972.

Sphingomonas paucimobilis NCIMB 8195 catalyzes an efficient deracemization of a wide range of secondary alcohols leading to up to 90% yield of the (R)-alcohol. The corresponding ketones were formed at various levels during each of the biotransformations, indicating that stereoinversion of the (S)-alcohol proceeds by sequential oxidation and reduction.
G. R. Allan, A. J. Carnell, J. Org. Chem., 2001, 66, 6495-6497.

A highly efficient dynamic kinetic resolution (DKR) of secondary alcohols at room temperature was developed. In situ racemization of substrates using a Ru catalyst and lipase-catalyzed acylation provides enantiopure products in high yields in very short reaction times. The use of isopropenyl acetate as the acyl donor makes the purification of the products very easy.
B. Martin-Matute, M. Edin, Krisztian Bogar, J.-E. Baeckvall, Angew. Chem. Int. Ed., 2004, 43, 6535-6539.

Well-defined 16-electron ruthenium complexes bearing an N-heterocyclic carbene ligand are active catalysts in the racemization of chiral alcohols. Mechanistic considerations are presented.
J. Bosson, S. P. Nolan, J. Org. Chem., 2010, 75, 2039-2043.