32507-39-4Relevant articles and documents
A donor-acceptor complex enables the synthesis of: E -olefins from alcohols, amines and carboxylic acids
Chen, Kun-Quan,Shen, Jie,Wang, Zhi-Xiang,Chen, Xiang-Yu
, p. 6684 - 6690 (2021/05/31)
Olefins are prevalent substrates and functionalities. The synthesis of olefins from readily available starting materials such as alcohols, amines and carboxylic acids is of great significance to address the sustainability concerns in organic synthesis. Metallaphotoredox-catalyzed defunctionalizations were reported to achieve such transformations under mild conditions. However, all these valuable strategies require a transition metal catalyst, a ligand or an expensive photocatalyst, with the challenges of controlling the region- and stereoselectivities remaining. Herein, we present a fundamentally distinct strategy enabled by electron donor-acceptor (EDA) complexes, for the selective synthesis of olefins from these simple and easily available starting materials. The conversions took place via photoactivation of the EDA complexes of the activated substrates with alkali salts, followed by hydrogen atom elimination from in situ generated alkyl radicals. This method is operationally simple and straightforward and free of photocatalysts and transition-metals, and shows high regio- and stereoselectivities.
Nickel-Catalyzed Carboxylation of Conjugated Dienes with Carbon Dioxide and DIBAL-H for the Synthesis of β,γ-Unsaturated Carboxylic Acids
Luo, Ying,Chan, Bun,Fukuda, Tsutomu,Onodera, Gen,Kimura, Masanari
supporting information, p. 1551 - 1554 (2021/01/21)
Conjugated dienes underwent Ni-catalyst-promoted 1,2-hydrocarboxylation in a 1:1 ratio with carbon dioxide under atmospheric pressure in the presence of diisobutylaluminum hydride (DIBAL-H) to give the corresponding β,γ-unsaturated carboxylic acids, without dimerization or oligomerization of the conjugated diene.
Ni-Catalyzed Regioselective Hydroarylation of 1-Aryl-1,3-Butadienes with Aryl Halides
Wang, Chengdong,Guo, Yingjie,Wang, Xiaoming,Wang, Zheng,Ding, Kuiling
supporting information, p. 15903 - 15907 (2021/10/07)
An efficient nickel-catalyzed regioselective hydroarylation of 1,3-dienes with aryl halides and a silane has been developed, affording a range of allylic arenes in good to excellent yields under mild conditions. This method exhibits broad substrate scope,
Palladium-Catalyzed Asymmetric Tandem Denitrogenative Heck/Tsuji-Trost of Benzotriazoles with 1,3-Dienes
Li, Yin-Lin,Wu, Hai-Hong,Zhang, Junliang,Zhang, Pei-Chao
supporting information, p. 13010 - 13015 (2021/09/07)
The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of asymmetric denitrogenative cycloaddition of benzotriazole with unsaturated hydrocarbons has been explored so far, bec
Cu-Catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-dienes with CO2
Zhang, Penglin,Zhou, Zhanglang,Zhang, Rumeng,Zhao, Qian,Zhang, Chun
supporting information, p. 11469 - 11472 (2020/10/12)
A practical copper-catalyzed highly regioselective 1,2-hydrocarboxylation of terminal 1,3-diene with carbon dioxide has been developed. Under mild reaction conditions, this chemistry afforded 2-benzyl-β,γ-unsaturated acid derivatives as products, which are a kind of important unit for bio-active molecules and versatile precursors for organic synthesis, with good functional group tolerance. The key intermediate in this transformation is illustrated by control experiments.
Nickel-catalyzed allyl-allyl coupling reactions between 1,3-dienes and allylboronates
Ji, Ding-Wei,He, Gu-Cheng,Zhang, Wei-Song,Zhao, Chao-Yang,Hu, Yan-Cheng,Chen, Qing-An
supporting information, p. 7431 - 7434 (2020/07/15)
A regiospecific allyl-allyl coupling reaction between 1,3-dienes and allylboronates has been demonstrated under nickel catalysis. Salient features of this method include the earth-abundant metal catalyst, excellent regioselectivity and good functional group tolerance. Notably, even congested allyl substrates can also be applied to this protocol, thus allowing for the rapid preparation of a series of valuable 1,5-dienes. This journal is
Stereoselective and Atom-Economic Alkenyl C-H Allylation/Alkenylation in Aqueous Media by Iridium Catalysis
Ding, Liyuan,Huang, Yinhua,Lu, Xiunan,Shen, Wenzhou,Xu, Liangyao,Yu, Feifei,Zhang, Jian,Zhong, Guofu,Zhong, Liangjun
, p. 7225 - 7237 (2020/07/07)
A practical and atom-economic protocol for the stereoselective preparation of various 1,4-and 1,3-diene skeletons through iridium-catalyzed directed olefinic C-H allylation and alkenylation of NH-Ts acrylamides in water was developed. This reaction tolerated a wide scope of substrates under simple reaction conditions and enabled successful gram-scale preparation. Furthermore, an asymmetric variant of this reaction giving enantioenriched 1,4-dienes was achieved employing a chiral diene-iridium complex as the catalyst.
Iron(III)/O2-Mediated Regioselective Oxidative Cleavage of 1-Arylbutadienes to Cinnamaldehydes
Bhowmik, Amit,Fernandes, Rodney A.
, p. 9203 - 9207 (2019/11/14)
A simple, efficient, and environmentally benevolent regioselective oxidative cleavage of 1-arylbutadienes to cinnamaldehydes mediated by iron(III) sulfate/O2 has been developed. The reaction offered good yields and excellent regioselectivity and showed good functional group tolerance (31 examples). The method is important, as few reports with limited substrate scope are available for such excellent oxidative cleavage of conjugated dienes.
In-chain functionalized syndiotactic 1,2-polybutadiene by a Ziegler-Natta iron(III) catalytic system
Liang, Shanshan,Zhang, Huaqiang,Cong, Rixin,Liu, Heng,Wang, Feng,Hu, Yanming,Zhang, Xuequan
, p. 33465 - 33471 (2019/10/28)
Copolymerization of 1,3-butadiene with four 1-substituted 1,3-diene comonomers bearing amino and alkyoxy groups by a Ziegler-Natta iron(iii) catalytic system to access in-chain functionalized syndiotactic 1,2-polybutadiene is reported herein. The polar co
Transition-Metal-Free Allylic Borylation of 1,3-Dienes
Maza, Ricardo J.,Davenport, Elliot,Miralles, Núria,Carbó, Jorge J.,Fernández, Elena
supporting information, p. 2251 - 2255 (2019/04/10)
This work explains the reactivity of diboron reagents with 1,3-dienes in a transition-metal-free context. The sole addition of Na2CO3 (30 mol %) to bis(pinacolato)diboron in MeOH allows the 1,4-hydroboration of cyclic and noncyclic 1,3-dienes. The electronic influence on the substrate guarantees the conjugated 1,4-hydroboration versus 1,2-diboration. DFT calculations show that the distribution of charge in the allylic anion intermediate governs the selectivity toward 1,4-hydroboration, while the favored trans configuration in diene reagents determines the preference for the E allyl boronate products.
