29291-01-8Relevant articles and documents
Electrochemical Semipinacol Rearrangements of Allylic Alcohols: Construction of All-Carbon Quaternary Stereocenters
Kang, Jun-Chen,Tu, Yong-Qiang,Dong, Jia-Wei,Chen, Chao,Zhou, Jia,Ding, Tong-Mei,Zai, Jian-Tao,Chen, Zhi-Min,Zhang, Shu-Yu
supporting information, p. 2536 - 2540 (2019/04/30)
The first examples of electrochemical trifluoromethylation and sulfonylation/semipinacol rearrangements of allylic alcohols were developed using cheap and stable RSO2Na (R = CF3, Ph) as reagents. Various β-trifluoromethyl and sulfonated ketones were obtained in moderate to excellent yields. This strategy provides a facile, direct, and complementary approach to construct all-carbon quaternary stereocenters. In addition, the reaction has the advantages of being chemical oxidant-free and metal-free and has safe and mild reaction conditions.
I2/Li2CO3-promoted cyanation of diarylalcohols through a dual activation process
Hu, Liangzhen,Hussain, Muhammad Ijaz,Deng, Qingfu,Liu, Qing,Feng, Yangyang,Zhang, Xiaohui,Xiong, Yan
, p. 308 - 314 (2018/12/11)
One-step base promoted strategy for cyanation of α,α-diaryl alcohols has been developed under mild and transition metal-free conditions. This method provides a straightforward and facile way towards the synthesis of β,γ-unsaturated nitriles and α-phenylnitiriles from α-vinyl carbinols and α,α-diaryl methanols, respectively, up to 99% yield. Moreover, various azides and ethers could also be accessed from their respective nucleophiles under standard reaction conditions.
Electrochemical Oxidative Aryl(alkyl)trifluoromethylation of Allyl Alcohols via 1,2-Migration
Guan, Zhipeng,Wang, Huamin,Huang, Yange,Wang, Yunkun,Wang, Shengchun,Lei, Aiwen
supporting information, p. 4619 - 4622 (2019/06/17)
An electrochemical oxidative difunctionalization of allyl alcohols for the synthesis of β-trifluoromethyl ketones is achieved through a 1,2-migration process. A series of β-trifluoromethyl ketones can be facilely obtained utilizing CF3SO2
α-Quaternary Mannich Bases through Copper-Catalyzed Amination-Induced 1,2-Rearrangement of Allylic Alcohols
Weng, Wei-Zhi,Sun, Jian-Guo,Li, Ping,Zhang, Bo
supporting information, p. 9752 - 9755 (2017/07/25)
A novel copper-catalyzed amination-induced 1,2-rearrangement reaction of allylic alcohols has been developed under simple and mild conditions. The commercially available N-fluorobenzenesulfonimide (NFSI) is employed as an amination reagent. In this transformation, not only alkyl, but also aryl substituents can efficiently undergo 1,2-carbon atom migration, thereby providing an efficient and powerful route to prepare a wide range of α-quaternary Mannich bases. The reaction features a broad substrate scope, operational simplicity, and excellent practicality.
Copper-catalyzed cyanomethylation of allylic alcohols with concomitant 1,2-aryl migration: Efficient synthesis of functionalized ketones containing an α-quaternary center
Bunescu, Ala,WangDr, Qian,Zhu, Jieping
supporting information, p. 3132 - 3135 (2015/04/14)
A copper-catalyzed alkylation of allylic alcohols by alkyl nitriles with concomitant 1,2-aryl migration was developed. Formation of the alkyl nitrile radical was followed by its intermolecular addition to alkenes and the migration of a vicinal aryl group with the concomitant generation of a carbonyl functionality to complete the domino sequence. Mechanistic studies suggested that 1,2-aryl migration proceeded through a radical pathway (neophyl rearrangement). The protocol provided an efficient route to functionalized ketones containing an α-quaternary center.
Palladium-catalyzed oxidative rearrangement of tertiary allylic alcohols to enones with oxygen in aqueous solvent
Li, Jingjie,Tan, Ceheng,Gong, Jianxian,Yang, Zhen
supporting information, p. 5370 - 5373 (2015/01/09)
A one-pot procedure for Pd(TFA)2-catalyzed 1,3-isomerization of tertiary allylic alcohols to secondary allylic alcohols followed by a Pd(TFA)2/neocuproine-catalyzed oxidative reaction to β-disubstituted-α,β-unsaturated kenones was developed. (Chemical Equation Presented).
Palladium-catalyzed oxidative rearrangement of diaryl alkenyl carbinols to β,β-diaryl α,β-unsaturated ketones
Rosa, David,Orellana, Arturo
supporting information; experimental part, p. 3648 - 3651 (2011/09/16)
An unusual oxidative palladium-catalyzed rearrangement of diaryl alkenyl carbinols to β,β-diaryl α,β-unsaturated ketones is described. The geometry of the alkene product is not determined by the electronic nature of the aryl substitutents but rather is determined by substitution pattern on the aryl rings. The reaction proceeds in good yields, utilizes oxygen at atmospheric pressure as the terminal oxidant, and tolerates a variety of functional groups on the aryl rings.
Titanocene-promoted eliminations on epoxy alcohols and epoxy esters
Fernandez-Mateos, Alfonso,Madrazo, Soledad Encinas,Teijon, Pablo Herrero,Gonzalez, Rosa Rubio
supporting information; experimental part, p. 856 - 861 (2010/04/05)
The reaction of a series of 2,3-epoxy alcohols and the corresponding formates, acetates, and benzoates promoted by Cp2TiCl has been studied. The different outcome of the reaction of epoxy derivatives has been rationalized in terms of mechanistically biased processes. After homolytic oxirane cleavage, four main types of reaction were found: dehydroxylation, decarboxylation, dehydrogenation, and deoxygenation. The reaction products varied according to the substitution pattern. The radical nature of these eliminations is demonstrated.
Reaction of tri- and tetrasubstituted alkenes with the low-temperature oxidizing system aluminum terf-butylate-terf-butyl hydroperoxide
Martynova,Stepovik,Dodonov
, p. 736 - 741 (2007/10/03)
The system consisting of aluminum tert-butylate and tert-butyl hydroperoxide under mild conditions (20°C) oxidizes tri- and tetrasubstituted ethylenes containing at least one α-methyl group. The reaction proceeds via formation of tertiary allylic hydroperoxides and their subsequent transformations into unsaturated alcohols and epoxy alcohols, and also into carbonyl compounds. The presence of the latter products suggests degradation of the carbon skeleton of alkenes.
