Article
Chemistry, Organic
Min Liu, Xing Wang, Ziqiong Guo, Hanyuan Li, Wei Huang, Hui Xu, Hui-Xiong Dai
Summary: In this study, the palladium-catalyzed asymmetric acyl-carbamoylation reaction was reported, producing alpha-quaternary chiral cycloketone with high yields and excellent enantioselectivity. The reaction proceeded via asymmetric 1,2-migratory insertions of acyl-Pd into alkenes and subsequent migratory insertion of isocyanides into C(sp(3))-Pd-II. The product could be further diversified, showcasing the synthetic utility of this protocol.
Article
Chemistry, Multidisciplinary
Xing Yang, Pankaj Kumar Majhi, Huifang Chai, Bin Liu, Jun Sun, Ting Liu, Yonggui Liu, Liejin Zhou, Jun Xu, Jiawei Liu, Dongdong Wang, Yanli Zhao, Zhichao Jin, Yonggui Robin Chi
Summary: This research introduces a novel catalytic strategy to modulate the thermodynamics and control the enantioselectivities of asymmetric aldol reactions via post-aldol processes. By using an NHC catalyst to activate a masked enolate substrate, the study successfully achieves enantioselective acylative kinetic resolution, resulting in acylated aldol products with high optical purities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Yang Sik Yun, Claudia E. Berdugo-Diaz, David W. Flaherty
Summary: Biomass has received considerable attention as an alternative to petrochemicals in the production of valuable chemicals and fuels. This Perspective discusses significant advancements in understanding the reaction networks and mechanisms, reactive intermediates, and active site motifs for selective production of desired compounds through hydrogenolysis over heterogeneous catalysts. Continuing research into hydrogenolysis reactions faces current challenges and provides opportunities for future exploration.
Article
Chemistry, Physical
Lantao Liu, Fangyuan Cheng, Chenxiang Meng, An-An Zhang, Mingliang Zhang, Kai Xu, Naoki Ishida, Masahiro Murakami
Summary: A Pd-catalyzed chemo-, regio-, and enantioselective ring-closing/ring-opening cross coupling reaction has been developed with diverse aryl halide-tethered alkenes and benzocyclobutenols as substrates. This method provides a convenient approach to chiral 2,3-dihydrobenzofurans with excellent enantioselectivities, and has been applied in the concise synthesis of analogues of cannabinoid receptor 2 agonists.
Article
Chemistry, Multidisciplinary
Stuart C. D. Kennington, Saul F. Teloxa, Miguel Mellado-Hidalgo, Oriol Galeote, Sabrina Puddu, Marina Bellido, Pedro Romea, Felix Urpi, Gabriel Aullon, Merce Font-Bardia
Summary: A direct and asymmetric aldol reaction of N-acyl thiazinanethiones with aromatic aldehydes catalyzed by chiral nickel(II) complexes was reported. The reaction gives high yields of O-TIPS-protected anti-aldol adducts with remarkable stereocontrol and atom economy. The removal of the achiral scaffold provides enantiomerically pure intermediates with synthetic interest for producing anti-alpha-amino-beta-hydroxy and alpha,beta-dihydroxy carboxylic derivatives, with theoretical calculations explaining the observed high stereocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yu-Qing Xiao, Miao-Miao Li, Zheng-Xin Zhou, Yu-Jie Li, Meng-Yue Cao, Xiao-Peng Liu, Hai-Hua Lu, Li Rao, Liang-Qiu Lu, Andre M. Beauchemin, Wen-Jing Xiao
Summary: This article describes a palladium-catalyzed highly diastereo- and enantioselective (3+2) cycloaddition reaction, which successfully synthesizes a variety of chiral five-membered heterocycles. The key to the success of this reaction is the remote stereoinduction through hydrogen bond, addressing the challenge of generating chiral quaternary stereocenters using substrates with two different acceptors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Doohyun Baek, Huijeong Ryu, Hyungwoo Hahm, Junseong Lee, Sukwon Hong
Summary: A highly enantioselective route to beta-quaternary (5-lactams) was described using palladium/pyridine-dihydroisoquinoline (PyDHIQ)-catalyzed conjugate arylations. The effect of pi-interactions on the enantioselectivity was elucidated, and the PyDHIQ ligand was found to play a crucial role in determining the enantioselectivity through attractive noncovalent interactions with substrates. The methodology was successfully applied to the asymmetric formal synthesis of (-)-picenadol.
Article
Chemistry, Physical
Runyou Ye, Maoshuai Zhu, Xufei Yan, Yang Long, Ying Xia, Xiangge Zhou
Summary: This study reveals a chelation-assisted palladium-catalyzed C=C bond cleavage reaction to form alkenyl nitrile, based on a formal group-exchange reaction. The isolated active Pd(II) complex and deuterium-labeled experiment confirm the necessity of the chelation group, proposing a plausible catalytic pathway.
Article
Chemistry, Multidisciplinary
Xuan Yu, Zining Zhang, Guangbin Dong
Summary: This study presents the discovery of a Rh-catalyzed enantioselective C-C activation involving migration of a sulfonyl radical. This unusual process transforms cyclobutanones containing a sulfonamide-tethered 1,3-diene moiety into gamma-lactams containing a beta-quaternary center with excellent enantioselectivity. The reaction exhibits broad functional group tolerance and a good substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Dong -Kai Wang, Liu-Bin Li, Fa-Liang Liu, Hui Qiu, Jiao-Zhe Li, Jianfeng Zhang, Chao Deng, Wen-Ting Wei
Summary: This study presents a novel method for the construction of all-carbon quaternary centers, specifically those with an alkyne-substituted framework, using a Fe-catalyzed formal insertion of diazo compounds into C(sp)-C(sp(3)) bonds of propargyl alcohols under mild conditions.
ACS CENTRAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Adrian Moreno Gonzalez, Kieran Nicholson, Natalia Llopis, Gary S. Nichol, Thomas Langer, Alejandro Baeza, Stephen P. Thomas
Summary: In this study, high oxidation-state carbonyl coupling partners were reacted with enones using two-fold organoborane catalysis to directly obtain aldol-type products. This new retrosynthetic disconnection method is compatible with enolisable coupling partners and achieves excellent chemoselectivity and substrate scope.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jinyu Zhang, Nuo Yan, Cheng-Wei Ju, Dongbing Zhao
Summary: A novel strategy involving Ni-0-catalyzed ring expansion process was developed for the preparation of enantioenriched silicon-stereogenic benzosiloles, with promising applications in chiral electronic and optoelectronic devices. The catalysis strategy was also successfully applied to the asymmetric synthesis of silicon-stereogenic bis-silicon-bridged pi-extended systems, showing fluorescence emission, Cotton effects, and circularly polarized luminescence (CPL) activity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Zong-Wang Qiu, Liang Long, Zhi-Qiang Zhu, Hong-Fu Liu, Han-Peng Pan, Ai-Jun Ma, Jin-Bao Peng, Yong-Heng Wang, Hao Gao, Xiang-Zhi Zhang
Summary: This study reports an efficient metal-free method for constructing acyclic all-carbon quaternary stereocenters. The asymmetric catalytic visible-light-induced Paterno-Buchi cycloaddition/electrocyclic ring-opening/alpha-selective arylation reactions of alpha,beta-unsaturated carbonyl compounds were successfully achieved via a well-designed reaction cascade. The method is applicable to a wide range of compounds and provides access to synthetically useful building blocks.
Article
Chemistry, Multidisciplinary
Xigong Liu, Changyin Zhao, Rongxiu Zhu, Lei Liu
Summary: The study presents a solution for constructing vicinal quaternary carbon stereocenters in acyclic systems, achieving excellent yields and selectivities through asymmetric cross-dehydrogenative coupling reactions. The generality of the approach was further demonstrated, and computational studies elucidated the origins of both diastereo- and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Teng Yuan, Kelton Radefeld, Chuan Shan, Carter Wegner, Erin Nichols, Xiaohan Ye, Qi Tang, Lukasz Wojtas, Xiaodong Shi
Summary: Here, we have reported an intermolecular asymmetric hydrative aldol reaction by using a vinyl-gold intermediate under ambient conditions. This reaction provides a base-free approach to β-hydroxy amides with high efficiency, yielding up to 95% and with over 50 examples. The use of vinyl gold intermediate as a reactive nucleophile and Fe(acac)(3) as a critical co-catalyst prevents undesired protodeauration, allowing the transformation to proceed under mild conditions with excellent functional group tolerance and stereoselectivity (>20:1 d.r. and up to 99% ee).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
