4.8 Article

Rh-catalyzed reagent-free ring expansion of cyclobutenones and benzocyclobutenones

Journal

CHEMICAL SCIENCE
Volume 6, Issue 10, Pages 5440-5445

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc01875g

Keywords

-

Funding

  1. CPRIT [R 1118]
  2. NIGMS [R01GM109054-01]
  3. Welch Foundation [F 1781]

Ask authors/readers for more resources

Here we report a reagent-free rhodium-catalyzed ring-expansion reaction via C-C cleavage of cyclobutenones. A variety of poly-substituted cyclopentenones and 1-indanones can be synthesized from simple cyclobutenones and benzocyclobutenones. The reaction condition is near pH neutral without additional oxidants or reductants. The potential for developing a dynamic kinetic asymmetric transformation of this reaction has also been demonstrated. Further study supports the proposed pathway involving Rh-insertion into the cyclobutenone C-C bond, followed by beta-hydrogen elimination, olefin insertion and reductive elimination.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.8
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

Review Chemistry, Multidisciplinary

Cyclobutenones and Benzocyclobutenones: Versatile Synthons in Organic Synthesis

Peng-hao Chen, Guangbin Dong

CHEMISTRY-A EUROPEAN JOURNAL (2016)

Article Polymer Science

Effect of Ring Functionalization on the Reaction Temperature of Benzocyclobutene Thermoset Polymers

Colin O. Hayes, Peng-hao Chen, R. Paxton Thedford, Christopher J. Ellison, Guangbin Dong, C. Grant Willson

MACROMOLECULES (2016)

Article Chemistry, Organic

Highly Diastereoselective α-Arylation of Cyclic Nitriles

Michael E. Dalziel, Penghao Chen, Diane E. Carrera, Haiming Zhang, Francis Gosselin

ORGANIC LETTERS (2017)

Article Chemistry, Physical

Cut and Sew Transformations via Transition-Metal-Catalyzed Carbon-Carbon Bond Activation

Peng-hao Chen, Brent A. Billett, Tatsuhiro Tsukamoto, Guangbin Dong

ACS CATALYSIS (2017)

Article Chemistry, Physical

Cobalt-Catalyzed Intramolecular Alkyne/Benzocyclobutenone Coupling: C-C Bond Cleavage via a Tetrahedral Dicobalt Intermediate

Zixi Zhu, Xinghan Li, Sicong Chen, Peng-hao Chen, Brent A. Billett, Zhongxing Huang, Guangbin Dong

ACS CATALYSIS (2018)

Article Multidisciplinary Sciences

Release and Degradation of Microencapsulated Spinosad and Emamectin Benzoate

Bin Bin Huang, Shao Fei Zhang, Peng Hao Chen, Gang Wu

SCIENTIFIC REPORTS (2017)

Article Chemistry, Multidisciplinary

Ruthenium-Catalyzed Reductive Cleavage of Unstrained Aryl-Aryl Bonds: Reaction Development and Mechanistic Study

Jun Zhu, Peng-hao Chen, Gang Lu, Peng Liu, Guangbin Dong

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

Article Chemistry, Multidisciplinary

Enabling Stable Cycling of 4.2 V High-Voltage All-Solid-State Batteries with PEO-Based Solid Electrolyte

Jiliang Qiu, Xinyu Liu, Rusong Chen, Qinghao Li, Yi Wang, Penghao Chen, Luyu Gan, Sang-Jun Lee, Dennis Nordlund, Yijin Liu, Xiqian Yu, Xuedong Bai, Hong Li, Liquan Chen

ADVANCED FUNCTIONAL MATERIALS (2020)

Article Radiology, Nuclear Medicine & Medical Imaging

Clinical Utility of F-18 Labeled Fibroblast Activation Protein Inhibitor (FAPI) for Primary Staging in Lung Adenocarcinoma: a Prospective Study

Youcai Li, Xinqing Lin, Yi Li, Jie Lv, Peng Hou, Shaoyu Liu, Penghao Chen, Min Wang, Chengzhi Zhou, Xinlu Wang

Summary: The study compared the primary staging of F-18 labeled fibroblast activation protein inhibitor ([F-18]F-FAPI) with that of F-18 labeled fluordesoxyglucose positron emission tomography/computed tomography ([F-18]F-FDG PET/CT) in patients with lung adenocarcinoma (LAD). The results showed that [F-18]F-FAPI PET/CT had a high detection rate for primary LAD and provided clearer tumor delineation and more lesions, especially in lymph nodes, the brain, and pleura. However, brain MRI could identify more and smaller lesions than [F-18]F-FAPI PET/CT.

MOLECULAR IMAGING AND BIOLOGY (2022)

Article Chemistry, Multidisciplinary

Raising the Intrinsic Safety of Layered Oxide Cathodes by Surface Re-Lithiation with LLZTO Garnet-Type Solid Electrolytes

Junyang Wang, Rusong Chen, Lufeng Yang, Mingwei Zan, Penghao Chen, Yu Li, Wenjun Li, Huigen Yu, Xiqian Yu, Xuejie Huang, Liquan Chen, Hong Li

Summary: Battery safety concerns have become more prominent as the demand for higher energy density lithium-ion batteries (LIBs) increases. This study demonstrates the use of solid electrolyte Li6.5La3Zr1.5Ta0.5O12 (LLZTO) to supply lithium ions to charged LiCoO2, effectively improving the safety performance of the battery.

ADVANCED MATERIALS (2022)

Meeting Abstract Chemistry, Multidisciplinary

Development of a highly diastereoselective α-arylation of cyclobutyl nitriles

Michael Dalziel, Penghao Chen, Diane Carrera, Haiming Zhang, Francis Gosselin

ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY (2017)

Meeting Abstract Chemistry, Multidisciplinary

Transition metal catalyzed carbon-carbon bond activation

Penghao Chen, Guangbin Dong

ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY (2015)

Meeting Abstract Chemistry, Multidisciplinary

Directly patternable polyhedral silsesqioxane and benzocyclobutene dielectric materials for microelectronics packaging

Colin Hayes, Philip Liu, Brennen Mueller, Penghao Chen, Paxton Thedford, William Bell, Paul Kohl, Guanbin Dong, Carlton Willson

ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY (2015)

Article Chemistry, Multidisciplinary

Iodide oxidation by ozone at the surface of aqueous microdroplets

Alexander M. Prophet, Kritanjan Polley, Gary J. Van Berkel, David T. Limmer, Kevin R. Wilson

Summary: The oxidation kinetics of iodide by ozone at the air-water interface is studied in single microdroplets. Molecular simulations and kinetic modeling are used to understand the underlying multiphase mechanism.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Aggregate assembly of ferrocene functionalized indium-oxo clusters

Rong Zhang, Jiajing Lan, Fei Wang, Shumei Chen, Jian Zhang

Summary: By utilizing 1,1'-ferrocene dicarboxylic acid as a chelating and surface protection ligand, we have synthesized multi-nuclear indium oxide clusters with varying nuclear sizes, including heptanuclear and thirteen-nuclear clusters. These clusters possess labile coordination sites, allowing for structural modification and self-assembly, resulting in the formation of various cluster structures.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Cucurbituril-based supramolecular host-guest complexes: single-crystal structures and dual-state fluorescence enhancement

Hui Wang, Hui Liu, Mingsen Wang, Jiaheng Hou, Yongjun Li, Yuancheng Wang, Yingjie Zhao

Summary: Two supramolecular complexes were prepared using CBs and M1, and their single-crystal structures were analyzed by SCXRD. The unexpected 1:2 self-assembly structure between M1 and CB[8] was discovered for the first time. These complexes exhibit unique photophysical properties and provide valuable information about the structure and photophysical properties of supramolecular complexes.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Engineering of cell-surface receptors for analysis of receptor internalization and detection of receptor-specific glycosylation

Chang-Hee Lee, Sookil Park, Sanggil Kim, Ji Young Hyun, Hyun Soo Lee, Injae Shin

Summary: The epidermal growth factor receptor (EGFR) is a cell-surface glycoprotein involved in cell proliferation and tumor development. This study used a fluorescently labeled EGFR to investigate its time-dependent endocytosis in live cells and found that appended glycans affect EGFR internalization. Additionally, the study detected sialic acid residues attached to EGFR on the live cell surface using FRET-based imaging. This research provides valuable insights into the cellular functions of EGFR.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Ultrasensitive detection of aromatic water pollutants through protein immobilization driven organic electrochemical transistors

Subhankar Sahu, Lokesh Kumar, Sumita Das, Dipti Gupta, Ruchi Anand

Summary: This study proposes a strategy that combines organic electronics with biosensor scaffolds to create a compact device for monitoring environmental aromatic pollution. By coupling biosensing protein MopR with an organic electrochemical transistor (OECT), a sensor module capable of efficient detection of phenol was designed. Exclusive phenol detection with minimal loss of sensitivity could be achieved in complex pollutant mixtures and real environmental samples.

CHEMICAL SCIENCE (2024)

Review Chemistry, Multidisciplinary

NiH-catalyzed C-N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons

Changseok Lee, Hyung-Joon Kang, Sungwoo Hong

Summary: The formation of C-N bonds through hydroamination reactions catalyzed by nickel hydrides has been a topic of recent interest. This approach offers a way to efficiently transform a variety of alkene and alkyne substrates into compounds enriched with C-N bonds. The review provides a concise overview of the underlying reaction mechanisms and aims to stimulate further progress in NiH-catalytic techniques and catalyst design.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Selective FRET nano probe based on carbon dots and naphthalimide-isatin for the ratiometric detection of peroxynitrite in drug-induced liver injury

Yueci Wu, Lu-Lu Sun, Hai-Hao Han, Xiao-Peng He, Weiguo Cao, Tony D. James

Summary: Drug-induced liver injury (DILI) is a common cause of acute liver failure in the USA and Europe, but most cases can be recovered or prevented by discontinuing the offending drug. Recent research has found that peroxynitrite (ONOO-) can be used as a potential indicator for early diagnosis of DILI, and there is an urgent need to establish a method to detect and track peroxynitrite in DILI cases. In this study, a FRET-based nano fluorescent probe CD-N-I was developed, which showed high selectivity and sensitivity in detecting peroxynitrite. The probe successfully detected exogenous peroxynitrite in live cells and endogenous peroxynitrite in APAP-induced liver injury of HepG2 cells.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Direct conversion of carboxylic acids to free thiols via radical relay acridine photocatalysis enabled by N-O bond cleavage

Dmitry L. Lipilin, Mikhail O. Zubkov, Mikhail D. Kosobokov, Alexander D. Dilman

Summary: This article describes a direct photocatalytic method for the thiolation of unprotected acids, which was previously challenging. By using a thionocarbonate reagent with an N-O bond, the efficient conversion of carboxylic acids to thiols is achieved.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Towards routine organic structure determination using Raman microscopy

Jason Malenfant, Lucille Kuster, Yohann Gagne, Kouassi Signo, Maxime Denis, Sylvain Canesi, Mathieu Frenette

Summary: Raman microscopy can reveal compound-specific vibrational fingerprints without sample preparation. The combination of efficient theoretical calculations and a user-friendly software can accurately predict peak positions and provide match scores to assist with structure determination.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Metal selectivity and translocation mechanism characterization in proteoliposomes of the transmembrane NiCoT transporter NixA from Helicobacter pylori

Jayoh A. Hernandez, Paul S. Micus, Sean Alec Lois Sunga, Luca Mazzei, Stefano Ciurli, Gabriele Meloni

Summary: Essential trace metals play crucial roles in the survival and virulence of bacterial pathogens. Helicobacter pylori requires nickel for colonization and persistence in the stomach, and NixA is an essential nickel transporter in this process. This study characterizes the selectivity and electrogenic nature of NixA-mediated nickel transport.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

A high-spin alkylperoxo-iron(III) complex with cis-anionic ligands: implications for the superoxide reductase mechanism

Tarali Devi, Kuheli Dutta, Jennifer Deutscher, Stefan Mebs, Uwe Kuhlmann, Michael Haumann, Beatrice Cula, Holger Dau, Peter Hildebrandt, Kallol Ray

Summary: This study emphasizes the importance of subtle electronic changes and secondary interactions in the stability of biologically relevant metal-dioxygen intermediates. It also shows that the role of the chloride ligand in stabilizing the Fe-III-(OOBu)-Bu-t moiety can extend to other anions, including the thiolate ligand.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Effects of altered backbone composition on the folding kinetics and mechanism of an ultrafast-folding protein

Jacqueline R. Santhouse, Jeremy M. G. Leung, Lillian T. Chong, W. Seth Horne

Summary: By studying the folding kinetics and mechanism of the BdpA sequence, researchers found that altering the backbone connectivity can affect protein folding. This suggests that protein mimetic chains have a significant degree of plasticity in transitioning between unfolded and folded states.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Strain induced reactivity of cyclic iminoboranes: the (2+2) cycloaddition of a 1H-1,3,2-diazaborepine with ethene

Divanshu Gupta, Ralf Einholz, Holger F. Bettinger

Summary: This study presents the first direct spectroscopic evidence of a cyclic seven-membered iminoborane. Compared to linear amino-iminoboranes, this cyclic iminoborane exhibits weakened bond strength and lower Lewis acidity value. The study suggests that the reduced ring strain of cyclic iminoborane prevents nitrogen fixation but allows facile (2 + 2) cycloaddition reaction with C2H4.

CHEMICAL SCIENCE (2024)

Article Chemistry, Multidisciplinary

Unveiling the topology of partially disordered micro-crystalline nitro-perylenediimide with X-aggregate stacking: an integrated approach

Renny Mathew, Aniruddha Mazumder, Praveen Kumar, Julie Matula, Sharmarke Mohamed, Petr Brazda, Mahesh Hariharan, Brijith Thomas

Summary: This study reveals the packing arrangement of partially disordered nitro-perylenediimide (NO2-PDI) using a synergistic approach that combines 3D ED, ssNMR, and DFT techniques. By overcoming these challenges, this methodology opens up new avenues for material characterization, driving exciting advancements in the field.

CHEMICAL SCIENCE (2024)