17488-64-1Relevant academic research and scientific papers
A vinyl radical cyclization route to hydroxycyclohexene fused carbocycles
Chaudhuri, Shiladitya,Maity, Susama,Roy, Mahua,Ray, Paramita,Ray, Jayanta K.
, p. 233 - 234 (2016)
Some hydroxycyclohexene fused carbocycles derivatives were synthesized from 6-bromo-hepta-1,5-dien-4-ol derivatives using a mediator, tri-n-butyltin hydride (TBTH) and an initiator, azobisisobutyronitrile (AIBN) in refluxing benzene.
Arene Trifunctionalization with Highly Fused Ring Systems through a Domino Aryne Nucleophilic and Diels–Alder Cascade
He, Jia,Jia, Zizi,Tan, Hongcheng,Luo, Xiaohua,Qiu, Dachuan,Shi, Jiarong,Xu, Hai,Li, Yang
supporting information, p. 18513 - 18518 (2019/11/19)
A convenient and efficient domino aryne process was developed under transition-metal-free conditions to generate a range of tetra- and pentacyclic ring systems. This transformation was realized via a 1,2-benzdiyne through a nucleophilic and Diels–Alder reaction cascade using styrene as the diene moiety. Three new chemical bonds, namely one C?N and two C?C bonds, and two benzofused rings could be constructed concomitantly, which was made possible by distinct chemoselective control at both the 1,2-aryne and 2,3-aryne stages. Moreover, in-depth studies were carried out on the domino aryne precursors and controlling the diastereoselectivity.
1,n-rearrangement of allylic alcohols promoted by hot water: Application to the synthesis of navenone B, a polyene natural product
Li, Pei-Fang,Wang, Heng-Lu,Qu, Jin
, p. 3955 - 3962 (2014/05/20)
It was reported for the first time that hot water as a mildly acidic catalyst efficiently promoted 1,n-rearrangement (n = 3, 5, 7, 9) of allylic alcohols. In some cases, the rearrangement reactions joined isolated C-C double or triple bonds to generate conjugated polyene or enyne structure motifs. We used the 1,3-rearrangement reaction of an allylic alcohol in hot water as part of an attractive new strategy for construction of the polyene natural product navenone B by iterative use of a Grignard reaction, a 1,3-rearrangement of the resulting allylic alcohol, and subsequent oxidation of the rearranged product.
Migratory dynamic kinetic resolution of carbocyclic allylic alcohols
Manzuna Sapu, Chicco,G?rbe, Tams,Lihammar, Richard,B?ckvall, Jan-E.,Deska, Jan
supporting information, p. 5952 - 5955 (2015/02/19)
A novel migratory dynamic kinetic resolution based on the interplay between an enzyme acylation catalyst and a heterogeneous Bronsted acid as an isomerization/racemization catalyst gives rise to carbocyclic allylic esters with excellent stereoselectivity
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).
From planning to optimization: Total synthesis of valerenic acid and some bioactive derivatives
Ramharter, Juergen,Mulzer, Johann
experimental part, p. 2041 - 2053 (2012/05/05)
A detailed study of the total synthesis of valerenic acid, a well known GABAA receptor subtype modulator, is described. Both successful as well as unsuccessful attempts towards the synthesis of the title compound are presented, including four different strategies to synthesize one of the key intermediates. The first two strategies are based on epoxides provided from the chiral pool, whereas the last two approaches rest on stereocontrolled modifications of 2-cyclopentenone. The streamlined synthesis implements a new one-pot reaction, which combines the addition of a Grignard species with an acid-catalyzed isomerization of the intermediate allylic alcohol. Further highlights are a stereo- and regioselective hydroxy-directed Diels-Alder reaction, a hydroxy-directed hydrogenation, and a final Negishi coupling reaction. After optimization of our synthesis, the preparation of several easily available derivatives is also discussed. Amides obtained by functionalization of the carboxyl group are more than twice as active as valerenic acid. The development and optimization of four different approaches towards valerenic acid (1) are described. The shortest approach spans 10 steps and provides valerenic acid in 25 % overall yield by incorporating a new one-pot reaction, an extremely stereo- and regioselective metal-coordinated Diels-Alder reaction, a hydroxy-directed hydrogenation, and a final Negishi coupling reaction. Copyright
Efficient synthesis of α,β-unsaturated alkylimines performed with allyl cations and azides: Application to the synthesis of an ant venom alkaloid
Hayashi, Kyohei,Tanimoto, Hiroki,Zhang, Huan,Morimoto, Tsumoru,Nishiyama, Yasuhiro,Kakiuchi, Kiyomi
supporting information, p. 5728 - 5731 (2013/01/15)
An efficient synthesis of α,β-unsaturated alkylimines at low temperature using azides has been developed. Carbocations generated from allyl alcohols helped achieve a rapid conversion under mild conditions with azides to afford reactive α,β-unsaturated imines. Hydroxy or alkoxy groups are essential for these transformations, and utilizing readily accessible allyl alcohols gave a wide extension of substrates. The efficiency of this novel method is demonstrated in the total synthesis of an iminium ant venom alkaloid.
Pt-catalyzed oxidative rearrangement of cyclic tertiary allylic alcohols to enones using aqueous hydrogen peroxide
Nagamine, Takashi,Kon, Yoshihiro,Sato, Kazuhiko
, p. 744 - 746 (2012/09/22)
An oxidative rearrangement of cyclic tertiary allylic alcohols to β-disubstituted α,β-unsaturated ketones by Pt black catalyst with aqueous hydrogen peroxide is described. The reaction proceeds under organic solvent- and halide-free conditions and gives only water as a coproduct. The Pt black catalyst is commercially available and can be reused at least four times.
Efficient and scalable one-Pot Synthesis of 2,4-Dienols from cycloalkenones: Optimized total synthesis of valerenic acid
Ramharter, Juergen,Mulzer, Johann
supporting information; experimental part, p. 5310 - 5313 (2011/12/04)
A mild and selective one-pot procedure to provide 2,4-dienols from simple cycloalkenones in high yields is described. This transformation is based on the in situ formation of acid-labile allylic alcohols, which on treatment with trifluoroacetic acid under
Mild and tunable benzoic acid catalysts for rearrangement reactions of allylic alcohols
McCubbin, J. Adam,Voth, Samantha,Krokhin, Oleg V.
experimental part, p. 8537 - 8542 (2011/12/14)
An efficient and simple catalytic method for the isomerization of readily prepared allylic alcohols is described. We focus particularly on cyclic examples and the synthesis of unusual enyne and dienols. The benzoic acid catalysts employed are commercially available and very inexpensive and can be tuned for reactivity and substrate sensitivity.
