Article
Chemistry, Applied
Timm Bury, Sven Kullmann, Bernhard Breit
Summary: Here, a highly branched regioselective nickel(0)-catalyzed hydrocyanation of mono- and 1,1-disubstituted allenes as well as an asymmetric hydrocyanation of 1,1-disubstituted allenes is reported, providing access to branched tertiary and quaternary beta,gamma-allylic nitriles. The regioselective hydrocyanation of terminal allenes using a nickel(0)/Biphephos catalytic system offers yields up to 96% and is applicable to a substrate scope containing various functional groups. The catalytic system of Ni(0)/TADDOL-based bisphosphite catalyst enables the synthesis of branched quaternary allylic nitriles with yields up to 99% and enantioselectivities up to 86%.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Yonggang Yan, Jinjin Sun, Gang Li, Liu Yang, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A light-promoted Ni-catalyzed cyanation reaction using 1,4-dicyanobenzene as a cyanating agent is described. Various aryl bromides, chlorides, and druglike molecules are converted to their corresponding nitriles (65 examples). Mechanistic studies reveal that under irradiation, the Ni(II)(dtbbpy)(p-C6H4CN)(CN) oxidative addition product undergoes homolytic cleavage of the Ni-aryl bond to generate an aryl radical and a Ni(I)-CN species, which initiates subsequent cyanation reactions.
Article
Chemistry, Physical
Jinguo Long, Shaomiao Xia, Ting Wang, Gui-Juan Cheng, Xianjie Fang
Summary: A regiodivergent cyanation of allylic alcohols under nickel catalysis was reported in this study, leading to the successful synthesis of challenging branched products. Dinitriles can also be obtained in good yields with high selectivity through subsequent hydrocyanation, which can be further functionalized into various compounds. Density functional theory (DFT) calculations provided insights into the role of ligands in tuning regioselectivity and reactivity.
Article
Chemistry, Physical
Ya-Fei Han, Yang Li, Xuan-Hui Ouyang, Ming Hu, Ze Tan, Jin-Heng Li
Summary: The nickel-catalyzed asymmetric reductive [3 + 2] annulation of o-haloaromatic beta-alkenyl ketones with alkynes enables the formation of highly enantiomerically enriched compounds with important structural and functional features. This reaction has a broad substrate scope and excellent selectivity, making it suitable for the synthesis of diverse chiral alcohol systems.
Article
Chemistry, Multidisciplinary
Zhonglin Liu, Lucas J. Oxtoby, Juntao Sun, Zi-Qi Li, Nana Kim, Geraint H. M. Davies, Keary M. Engle
Summary: The site-selective palladium-catalyzed three-component coupling of unactivated alkenyl carbonyl compounds, aryl- or alkenylboronic acids, and N-fluorobenzenesulfonimide is described in this study. Regioselectivity is enhanced by tuning the steric environment on the bidentate directing auxiliary, facilitating challenging C(sp(3))-F reductive elimination from a Pd-IV intermediate to afford 1,2-carbofluorination products in moderate to good yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bastian Muriel, Jerome Waser
Summary: A radical-mediated amination of cyclopropenes is reported, leading to tetrasubstituted alkenyl nitrile derivatives and allowing for the one-pot synthesis of highly functionalized polycyclic aromatic compounds. This transformation enables the synthesis of nitrile-substituted alkenes and aromatic compounds from readily available cyclopropenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Chang-Sheng Wang, Yongqi Yu, Yusuke Sunada, Chen Wang, Naohiko Yoshikai
Summary: This article reports a cobalt-catalyzed carbo- and hydrocyanation reaction of alkynes, which involves C-CN bond cleavage of organic cyanides. A low-valent cobalt-diphosphine catalyst, generated by reduction with Zn, is used to promote the arylcyanation of alkynes with trans-selectivity. Additionally, the addition of Zn(OTf)2 to the catalytic system accelerates the reaction and switches the stereoselectivity.
Article
Chemistry, Multidisciplinary
Katsumasa Tanaka, Hiroshi Hattori, Ryota Yabe, Takahiro Nishimura
Summary: In this study, an iridium-catalyzed sp(3) C-H alkylation reaction was conducted to achieve high yields in the reaction between N-methyl groups and 1,5- and 1,6-dienes, resulting in the formation of five- and six-membered carbocyclic compounds. The use of a chiral bidentate phosphine ligand allowed for the asymmetric synthesis of cyclic compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Sa-Na Yang, Shao-Han Sun, Chang -Hui Liu, Xiang -Ting Min, Boshun Wan, Ding -Wei Ji, Qing-An Chen
Summary: A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earth-abundant nickel catalyst. The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with (RO)(2)P(O)-Ni-H or R2P(O)O-Ni-H species, respectively. This research highlights the ability to access different regioisomers by diverting common elementary reaction steps.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Physical
Dongshun Ni, M. Kevin Brown
Summary: A Ni-catalyzed silylacylation of alkenes is introduced, providing rapid access to beta-silyl ketones by combining alkenes, CIZnSiR3, and acid chlorides. The method involves a catalytic intermediate of [Ni]-SiR3 complex, which is rare for three-component alkene functionalization. The synthetic utility of the products is demonstrated, along with detailed mechanistic descriptions.
Article
Chemistry, Organic
Mengna Liu, Benqiang Cui, Chuntao Zhong, Yanhui Shi, Yanfeng Dang, Changsheng Cao
Summary: A palladium-catalyzed cyanation of aryl dimethylsulfonium salts using K-4[Fe-(CN)(6)]center dot 3H(2)O as the cyanating reagent was successfully developed. The reaction proceeded under base-free conditions and yielded aryl nitriles with up to 92% yields. The protocol also allowed direct transformation of aryl sulfides to aryl nitriles, and the reaction mechanism was investigated using density functional theory calculations.
Article
Chemistry, Organic
Xinpeng Jiang, Zicong Zheng, Yan Gao, Deyou Lan, Wenhao Xu, Wang Zhang, Guofei Chen
Summary: This study reported a metal-free synthesis method for producing methylenecyclobutane containing tetrasubstituted alkenyl nitriles using a strain-release driven addition reaction of [1.1.1]propellane. The protocol could be scaled up to gram quantities and the resulting alkenyl nitriles were capable of undergoing various derivatization reactions, offering a wide range of possible transformation reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Zi-Hao Chen, Rui-Ze Sun, Fei Yao, Xu-Dong Hu, Long-Xue Xiang, Hengjiang Cong, Wen-Bo Liu
Summary: The study presents an enantioselective nickel-catalyzed intramolecular reductive cross-coupling reaction to assemble CN-containing all-carbon quaternary stereocenters by desymmetrizing cyclization of aryl/alkenyl halide-tethered malononitriles. The use of an organic reductant is crucial for the selectivity and reactivity, with demonstrated applications in the synthesis of bioactive molecules and natural products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Akira Saito, Shinya Adachi, Naoya Kumagai, Masakatsu Shibasaki
Summary: The strategic use of a sterically demanding Ni-II pincer carbene complex has enabled high enantioselectivity in the direct catalytic asymmetric addition of acetonitrile to aldehydes, resulting in highly enantioenriched beta-hydroxynitriles. This highly atom-economical process offers a promising pathway for utilizing inexpensive acetonitrile as a C2 building block in practical synthetic toolbox for asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Joss Pepe Strache, Lukas Muenzer, Andreas Adler, Dirk Blunk, Hans-Guenther Schmalz
Summary: We investigated the enantioselective Ni-catalyzed hydrocyanation of 1,3-diarylpropenes. A series of (E)-homostilbenes were prepared by Pd-catalyzed coupling, and the hydrocyanation of various homostilbenes was studied using a Ni(cod)2/TADDOL-derived chiral phosphine-phosphite ligand catalyst system. The methodology was applied in a short synthesis of a colchicine analogue, and the absolute configuration of 2,4-diphenylbutyronitrile was determined by comparing experimental and calculated ECD spectra.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jihui Gao, Mingdong Jiao, Jie Ni, Rongrong Yu, Gui-Juan Cheng, Xianjie Fang
Summary: A regiodivergent nickel-catalyzed hydrocyanation of a broad range of internal alkenes with high regioselectivities is reported, achieving either linear or branched nitriles with good yields. DFT calculations showed that the catalyst architecture plays a crucial role in determining regioselectivity by modulating electronic and steric interactions. Additionally, moderate enantioselectivities were observed in the production of branched nitriles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Rongrong Yu, Yidan Xing, Xianjie Fang
Summary: A regio-, chemo-, and enantioselective nickel-catalyzed hydrocyanation of 1,3-dienes has been achieved by using a specific multichiral diphosphite ligand. Besides aryl-substituted 1,3-dienes, challenging aliphatic 1,3-diene substrates can also be selectively converted to the corresponding 1,2-adducts with high yields and the highest enantioselectivities to date.
Article
Chemistry, Organic
Jihui Gao, Jie Ni, Rongrong Yu, Gui-Juan Cheng, Xianjie Fang
Summary: This highly regioselective nickel-based catalyst system enables the isomerization/hydrocyanation of aliphatic internal olefins, providing a variety of aliphatic nitriles with excellent regioselectivities and good yields under mild conditions. The reaction protocol, under Lewis acid-free conditions, shows broad functional group tolerance, including secondary amine and unprotected alcohol groups.
Article
Chemistry, Organic
Feilong Sun, Chengxi Yang, Jie Ni, Gui-Juan Cheng, Xianjie Fang
Summary: A regiodivergent nickel-catalyzed hydrocyanation of 1-aryl-4-silyl-1,3-diynes is reported, where appropriate ligands result in high yields and regioselectivities of two different enynyl nitriles. DFT calculations show that different ligands lead to diverse alkyne insertion modes, impacting the regioselectivity. The synthetic value of cyano-containing 1,3-enynes is demonstrated through downstream transformations.
Article
Chemistry, Organic
Ying Ding, Jinguo Long, Feilong Sun, Xianjie Fang
Summary: A nickel-catalyzed isomerization/allylic cyanation of alkenyl alcohols is reported, providing a new complement to allylic substitution reactions. The use of a specific diphosphite ligand and methanol as the solvent is crucial for the success of this transformation, as demonstrated by a gram-scale regioconvergent experiment and formal synthesis of quebrachamine showcasing the high potential of this methodology.
Article
Chemistry, Physical
Feilong Sung, Ting Wang, Gui-Juan Cheng, Xianjie Fang
Summary: A nickel-catalyzed enantioselective hydrocyanation of N-aryl 5-norbornene-endocis-2,3-dicarboximides was reported, allowing for the quick construction of stereogenic carbon centers and remote N-C-Ar atropisomeric chirality. Mechanism studies revealed that the resident carbonyl group of the substrates plays a critical role in the enantioselectivity.
Article
Chemistry, Physical
Jinguo Long, Shaomiao Xia, Ting Wang, Gui-Juan Cheng, Xianjie Fang
Summary: A regiodivergent cyanation of allylic alcohols under nickel catalysis was reported in this study, leading to the successful synthesis of challenging branched products. Dinitriles can also be obtained in good yields with high selectivity through subsequent hydrocyanation, which can be further functionalized into various compounds. Density functional theory (DFT) calculations provided insights into the role of ligands in tuning regioselectivity and reactivity.
Article
Chemistry, Multidisciplinary
Rongrong Yu, Song-Zhou Cai, Can Li, Xianjie Fang
Summary: In this study, a nickel-catalyzed asymmetric carbonylation reaction was reported for the rapid construction of polysubstituted cyclopropanecarboxylic derivatives. The method exhibited high atom economy, good functional group tolerance, and excellent diastereo- and enantioselectivity. The synthetic utility of the method was demonstrated by facile conversion of the chiral products into bioactive molecules such as (-)-Tranylcypromine and (-)-Lemborexant.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Mingdong Jiao, Xianjie Fang
Summary: A novel synthesis of homoallylic nitriles via cobalt-catalyzed hydrocyanation of methylenecyclopropanes is described. The protocol demonstrates excellent selectivity, mild reaction conditions, good functional group compatibility, gram-scale reaction, and product transformations. The extraordinary selectivity is probably attributed to the stronger aptitude of the alkyl-cobalt cyanide intermediate for reductive elimination rather than beta-hydride elimination.
Article
Chemistry, Multidisciplinary
Jinguo Long, Ruihua Zhao, Gui-Juan Cheng, Xianjie Fang
Summary: A palladium-catalyzed hydrocyanation of propiolamides for the stereodivergent synthesis of trisubstituted acrylonitriles is described. The method can tolerate various primary, secondary, and tertiary propiolamides. The selection of a suitable ligand is crucial for the success of this stereodivergent process. Control experiments indicate the intermediacy of E-acrylonitriles, which undergo isomerization to form Z-acrylonitriles. Density functional theory calculations suggest that the bidentate ligand L2 enables a feasible cyclometallation/isomerization pathway for the E to Z isomerization, while the monodentate ligand L1 inhibits the isomerization, leading to divergent stereoselectivity. The usefulness of this method is demonstrated by the facile derivatization of products to give various E- and Z-trisubstituted alkenes. Additionally, the E- and Z-acrylonitrile products have been successfully employed in cycloaddition reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Can Li, Rongrong Yu, Song-Zhou Cai, Xianjie Fang
Summary: We have developed a highly diastereoselective method for the synthesis of cyano-substituted cyclopropanes using palladium-catalyzed direct cyanoesterification of cyclopropenes. This method offers mild reaction conditions, good functional group compatibility, and simple operation. The transformation described in this study provides a stepwise, highly atom economic, and scalable approach for obtaining synthetically useful cyclopropanecarbonitriles.
Article
Chemistry, Organic
Song-Zhou Cai, Rongrong Yu, Can Li, Hongyu Zhong, Xichang Dong, Bill Morandi, Juntao Ye, Xianjie Fang
Summary: Hydrothiocarbonylation of olefins using carbon monoxide and thiols is a powerful method to synthesize thioesters. However, transition-metal-catalyzed asymmetric thiocarbonylation, particularly with earth abundant metals, is rarely reported. In this study, a nickel-catalyzed enantioselective hydrothiocarbonylation of cyclopropenes was developed for the synthesis of functionalized thioesters with high stereoselectivity.
Article
Chemistry, Organic
Ying Ding, Jinguo Long, Xianjie Fang
Summary: A nickel-catalyzed hydrocyanation of aliphatic allenes with excellent regioselectivity has been developed. This protocol features mild reaction conditions and good functional group tolerance, providing an efficient catalytic pathway to access various allylic nitriles containing quaternary carbon centers in a one-step fashion. Additionally, preliminary attempts were made to investigate an asymmetric version of this reaction.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Feilong Sun, Jihui Gao, Xianjie Fang
CHEMICAL COMMUNICATIONS
(2020)
