- Synthesis of 1-Tri(di)fluoromethyl 1,4-Diketones Enabled by Radical Brook Rearrangement
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Herein, we disclose the first and simple one-pot-two-step process to the synthesis of 1-difluoromethyl 1,4-diketones, through Mn-catalyzed radical Brook rearrangement. The methodology is also amenable to the synthesis of 1-trifluoromethyl 1,4-diketones. T
- Chen, Xiang,Liu, Shanshan,Shen, Xiao,Zhang, Jianjun,Zhu, Zhihong
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supporting information
p. 4927 - 4931
(2021/09/30)
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- Photo-induced phosphorus radical involved semipinacol rearrangement reaction: Highly synthesis of γ-oxo-phosphonates
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Hydroxyphosphoric acids display the unique biological activities, and they have some attractive prospects as clinical drug moleculars. Herein, a new approach for the synthesis of γ-oxo-phosphonates (the precursor of hydroxyphosphoric acid) has been established through the semipinacol rearrangement tactic involved the photo-induced phosphorus radical process. Most important, this transformation is avoid of the external oxidants, and occurs very well under the sunlight irradiation, meanwhile the γ-oxo-phosphonate was easily derivatized to obtain γ-hydroxyphosphoric acid, thus highlights the synthesis value of this method.
- Wang, Chunhai,Huang, Xiaoling,Liu, Xueting,Gao, Suqian,Zhao, Bin,Yang, Shangdong
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p. 677 - 680
(2019/08/27)
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- I2/Li2CO3-promoted cyanation of diarylalcohols through a dual activation process
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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.
- Hu, Liangzhen,Hussain, Muhammad Ijaz,Deng, Qingfu,Liu, Qing,Feng, Yangyang,Zhang, Xiaohui,Xiong, Yan
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p. 308 - 314
(2018/12/11)
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- Organoiodine-Catalyzed Enantioselective Alkoxylation/Oxidative Rearrangement of Allylic Alcohols
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An enantioselective catalytic alkoxylation/oxidative rearrangement of allylic alcohols has been established by using a Br?nsted acid and chiral organoiodine. The presence of 20 mol % of an (S)-proline-derived C2-symmetric chiral iodine led to enantioenriched α-arylated β-alkoxylated ketones in good yields and with high levels of enantioselectivity (84–94 % ee).
- Zhang, Dong-Yang,Zhang, Ying,Wu, Hua,Gong, Liu-Zhu
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supporting information
p. 7450 - 7453
(2019/05/10)
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- Electrochemical Oxidative Aryl(alkyl)trifluoromethylation of Allyl Alcohols via 1,2-Migration
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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
- Guan, Zhipeng,Wang, Huamin,Huang, Yange,Wang, Yunkun,Wang, Shengchun,Lei, Aiwen
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supporting information
p. 4619 - 4622
(2019/06/17)
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- Oxidative acylation of α,α-diarylallylic alcohols: Synthesis of 1,2,4-triarylbutane-1,4-diones
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A metal-free mediated oxidative acylation of α,α-diarylallylic alcohols with simple aromatic aldehydes for the synthesis of 1,2,4-triphenylbutane-1,4-diones is presented. In the presence of TBPB (tert-butyl peroxybenzoate), desired products were obtained in good to excellent yields for 28 examples. This protocol features high regioselectivity, wide functional group tolerance and atom economy.
- Li, Yong,Leng, Yuting,Wang, Shiwei,Gao, Yuhui,Lv, Huiyan,Chang, Junbiao,Wu, Yusheng,Wu, Yangjie
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- Tandem SN2′ nucleophilic substitution/oxidative radical cyclization of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds
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A novel and efficient tandem SN2′ nucleophilic substitution/oxidative radical cyclization reaction of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds has been developed by using Mn(OAc)3 as an oxidant, which enables t
- Zhang, Zhen,Li, Cheng,Wang, Shao-Hua,Zhang, Fu-Min,Han, Xue,Tu, Yong-Qiang,Zhang, Xiao-Ming
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p. 3239 - 3247
(2017/04/24)
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- Iron-promoted difunctionalization of alkenes by phenylselenylation/1,2-aryl migration
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Iron-promoted difunctionalization of α,α-diaryl and α-aryl-α-alkyl allylic alcohols has been efficiently achieved by means of N-(phenylseleno)phthalimide (N-PSP) under mild conditions. An in situ generated phenylselenium cation (PhSe+) was added to the ol
- Wu, Ping,Wu, Kaikai,Wang, Liandi,Yu, Zhengkun
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supporting information
p. 5450 - 5453
(2017/11/06)
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- Dual Catalysis Using Boronic Acid and Chiral Amine: Acyclic Quaternary Carbons via Enantioselective Alkylation of Branched Aldehydes with Allylic Alcohols
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A ferrocenium boronic acid salt activates allylic alcohols to generate transient carbocations that react with in situ-generated chiral enamines from branched aldehydes. The optimized conditions afford the desired acyclic products embedding a methyl-aryl quaternary carbon center with up to 90% yield and 97:3 enantiomeric ratio, with only water as the byproduct. This noble-metal-free method complements alternative methods that are incompatible with carbon-halogen bonds and other sensitive functional groups.
- Mo, Xiaobin,Hall, Dennis G.
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supporting information
p. 10762 - 10765
(2016/09/09)
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- UV light-mediated difunctionalization of alkenes through aroyl radical addition/1,4-/1,2-Aryl shift cascade reactions
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UV light-mediated difunctionalization of alkenes through an aroyl radical addition/1,4-/1,2-aryl shift has been described. The resulted aroyl radical from a photocleavage reaction added to acrylamide compounds followed by cyclization led to the formation of oxindoles, whereas the addition to cinnamic amides aroused a unique 1,4-aryl shift reaction. Furthermore, the difunctionalization of alkenes of prop-2-en-1-ols was also achieved through aroyl radical addition and a sequential 1,2-aryl shift cascade reaction.
- Zheng, Lewei,Huang, Hongli,Yang, Chao,Xia, Wujiong
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p. 1034 - 1037
(2015/03/30)
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- Synthesis and SAR study of diphenylbutylpiperidines as cell autophagy inducers
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A novel series of diphenylbutylpiperidines as autophagy inducers was described and extensive SAR studies resulted in derivatives (15d-e, 15i-j) with 10-fold greater activity than the lead compounds 1 and 2. Meanwhile, a new synthetic route to diphenylbutyl bromide (6) from bromobenzene and γ-butyrolactone was also reported here.
- Chen, Gang,Xia, Hongguang,Cai, Yu,Ma, Dawei,Yuan, Junying,Yuan, Chengye
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supporting information; experimental part
p. 234 - 239
(2011/02/26)
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- Rhodium catalyzed hydroformylation of 1,1-bis(p-fluorophenyl)allyl or propargyl alcohol: A key step in the synthesis of Fluspirilen and Penfluridol
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Fluspirilen (1) and Penfluridol (2), two neuroleptic agents, belong to a wide class of pharmaceuticals that contain in their molecules a 4,4-bis(p-fluorophenyl)butyl group bound to a nitrogen atom of a pyrrolidine, piperidine or piperazine moiety. A key intermediate for the synthesis of compounds 1 and 2,4,4-bis(p-fluorophenyl)butylbromide (15), has been prepared starting from commercially available 4,4′-difluorobenzophenone (7) following a preparative route involving the rhodium catalyzed hydroformylation in toluene or in the biphasic system toluene/water or cyclohexane/water of 1,1-bis(p-fluorophenyl)-2-propenol (8) and/or 1,1-bis(p-fluorophenyl)-2-propynol (12). Fluspirilen and Penfluridol were obtained in 70-80% yield by reaction of bromide 15 with 1-phenyl-1,3,8-triazaspiro[4,5]decan-4-one (16) and 4-[4-chloro-3-(trifluoromethyl)phenyl]-4-piperidinol (17), respectively. The overall yields of the two pharmaceuticals 1 and 2, based on starting ketone 7, were about 35-40%.
- Botteghi, Carlo,Marchetti, Mauro,Paganelli, Stefano,Persi-Paoli, Francesco
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p. 1631 - 1637
(2007/10/03)
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