7428-99-1Relevant articles and documents
Conjugated elimination versus [1,2]-Wittig rearrangement of unsaturated diox(ol)anes
Lemiègre, Lo?c,Regnier, Thomas,Combret, Jean-Claude,Maddaluno, Jacques
, p. 373 - 377 (2003)
A set of unsaturated dioxanes and dioxolanes has been prepared in three steps from acetoxy-1-isoprene. When reacted with two equivalents of t-BuLi in THF, these compounds provided, under various conditions, a mixture of two types of 1,3-dienes. The first one, derived from a conjugated elimination reaction resulting in the heterocycles opening, is relatively unstable but could be trapped as an acrylate. The second one resulted probably from a [1,2]-Wittig rearrangement. The competition between these two reactions has been observed for both dioxanes and dioxolanes (but not for acyclic ketals) and is the object of a strong temperature effect, the Wittig rearrangement being favored over the elimination at room temperature. A difference between kinetic and thermodynamic deprotonation sites is proposed to be at the origin of this competition on the base of both experimental and theoretical results.
Expeditious and practical synthesis of tertiary alcohols from esters enabled by highly polarized organometallic compounds under aerobic conditions in Deep Eutectic Solvents or bulk water
Quivelli, Andrea F.,D'Addato, Giovanna,Vitale, Paola,García-álvarez, Joaquín,Perna, Filippo M.,Capriati, Vito
, (2021/01/18)
An efficient protocol was developed for the synthesis of tertiary alcohols via nucleophilic addition of organometallic compounds of s-block elements (Grignard and organolithium reagents) to esters performed in the biodegradable choline chloride/urea eutectic mixture or in water. This approach displays a broad substrate scope, with the addition reaction proceeding quickly (20 s reaction time) and cleanly, at ambient temperature and under air, straightforwardly furnishing the expected tertiary alcohols in yields of up to 98%. The practicability of the method is exemplified by the sustainable synthesis of some representative S-trityl-L-cysteine derivatives, which are a potent class of Eg5 inhibitors, also via telescoped one-pot processes.
Efficient and selective oxidation of tertiary benzylic C[sbnd]H bonds with O2 catalyzed by metalloporphyrins under mild and solvent-free conditions
Hu, Meng-Yun,Liu, Lei,Qi, Bei,She, Yuan-Bin,Shen, Hai-Min,Ye, Hong-Liang
, (2020/05/19)
The direct and efficient oxidation of tertiary benzylic C[sbnd]H bonds to alcohols with O2 was accomplished in the presence of metalloporphyrins as catalysts under solvent-free and additive-free conditions. Based on effective inhibition on the unselective autoxidation and deep oxidation, systematical investigation on the effects of porphyrin ligands and metal centers, and apparent kinetics study, the oxidation system employing porphyrin manganese(II) (T(2,3,6-triCl)PPMn) with bulkier substituents as catalyst, was regarded as the most promising and efficient one. For the typical substrate, the conversion of cumene could reach up to 57.6% with the selectivity of 70.5% toward alcohol, both of them being higher than the current documents under similar conditions. The superiority of T(2,3,6-triCl)PPMn was mainly attributed to its bulkier substituent groups preventing metalloporphyrins from oxidative degradation, its planar structure favoring the interaction between central metal with reactants, and the high efficiency of Mn(II) in the catalytic transformation of hydroperoxides to alcohols.
Arylboronic Acid Catalyzed C-Alkylation and Allylation Reactions Using Benzylic Alcohols
Estopi?á-Durán, Susana,McLean, Euan B.,Donnelly, Liam J.,Hockin, Bryony M.,Taylor, James E.
supporting information, p. 7547 - 7551 (2020/10/09)
The arylboronic acid catalyzed dehydrative C-alkylation of 1,3-diketones and 1,3-ketoesters using secondary benzylic alcohols as the electrophile is reported, forming new C-C bonds (19 examples, up to 98% yield) with the release of water as the only byproduct. The process is also applicable to the allylation of benzylic alcohols using allyltrimethylsilane as the nucleophile (12 examples, up to 96% yield).
Method for selectively oxidizing cumene compounds
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Paragraph 0097; 0098, (2019/11/21)
The invention relates to a method for selectively oxidizing cumene compounds, and the method comprises the following steps: placing cumene compounds shown in a formula (I), an iron porphyrin catalyst,an oxidant and a dispersant into a ball milling tank, sealing the ball milling tank, performing ball milling for 3 to 24 hours at a rotating speed of 100 to 800 rpm at room temperature, stopping ballmilling once every 1 to 3 hours in the ball milling process, discharging gases in the ball milling tank, finishing the reaction, and performing post-treatment on a reaction mixture to obtain product2-phenyl-2-propanol compound shown in a formula (II); according to the invention, the oxidation conversion of the cumene and derivatives thereof is realized through solid-phase ball milling, the reaction mode is novel, the operation is convenient, and the energy consumption is low; the method needs no organic solvent, thus effectively avoiding the use of toxic and harmful organic solvents and being green and environment-friendly; has low peroxide content and high safety factor, and high 2-phenyl-2-propanol and derivative selectivity and meets the social requirements of the current green chemical process, environmental compatibility chemical process and biological compatibility chemical process.
COMPOUNS, COMPOSITIONS AND METHODS OF USE
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Page/Page column 137; 138, (2018/07/29)
Herein, compounds, compositions and methods for modulating inclusion formation and stress granules in cells related to the onset of neurodegenerative diseases, musculoskeletal diseases, cancer, ophthalmological diseases, and viral infections are described.
COMPOUNDS, COMPOSITIONS AND METHODS OF USE AGAINST STRESS GRANULES
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Paragraph 0911; 0912; 0934; 0935, (2018/11/21)
Herein, compounds, compositions and methods for modulating inclusion formation and stress granules in cells related to the onset of neurodegenerative diseases, musculoskeletal diseases, cancer, ophthalmological diseases, and viral infections are described.
COMPOUNDS, COMPOSITIONS AND METHODS OF USE
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Page/Page column 55; 97, (2018/11/22)
Herein, compounds, compositions and methods for modulating inclusion formation and stress granules in cells related to the onset of neurodegenerative diseases, musculoskeletal diseases, cancer, ophthalmological diseases, and viral infections are described.
Catalytic Direct-Type Addition Reactions of Alkylarenes with Imines and Alkenes
Yamashita, Yasuhiro,Suzuki, Hirotsugu,Sato, Io,Hirata, Tsubasa,Kobayashi, Shū
supporting information, p. 6896 - 6900 (2018/05/14)
Catalytic addition reactions of very weakly acidic nonactivated alkylarenes such as toluene and its derivatives were developed by using a strongly basic mixed catalyst system under mild reaction conditions. The addition reactions with imines and alkenes proceeded smoothly under proton-transfer conditions to afford the desired products in good to high yields, and high levels of regio- and stereoselectivity were achieved. It was also revealed that the asymmetric addition reaction of an alkylarene was possible.
Ligand-Free, Copper-Catalyzed Aerobic Benzylic sp 3 C-H Oxygenation
Tanaka, Hirotaka,Oisaki, Kounosuke,Kanai, Motomu
, p. 1576 - 1580 (2017/08/11)
A ligand-free and operationally simple copper-catalyzed aerobic benzylic sp 3 C-H oxygenation was developed. The addition of tert -butyl hydroperoxide, either in a catalytic or stoichiometric amount, was key for activating stable C-H bonds under mild conditions to furnish the corresponding ketones or esters in moderate to excellent yield.
