rhodium-catalyzed c−h functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/rhodium... ·...

Rhodium-Catalyzed C−H Functionalization and Seven-membered Ring Formation Reporter: Dai Lu Supervisor: Prof. Zhao Jing Dr. Hong Mei 2013-12-23

Upload: others

Post on 23-Jul-2020

13 views

Category:

Documents

5 download

Report

Download

Embed Size (px):

TRANSCRIPT

Page 1: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

Rhodium-Catalyzed C−H Functionalization and Seven-membered Ring Formation

Reporter: Dai Lu Supervisor: Prof. Zhao Jing Dr. Hong Mei

2013-12-23

Page 2: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

Page 3: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

Different Annulation Options for o-Vinylphenols

three different C−H positions

2-hydroxystyrene

chromene-type molecules

benzofuranes

Morimoto, K.; Hirano, K.; Satoh, T.; Miura, M. J. Org. Chem. 2011, 76, 9548−9551.

oxepines

A Formal (5 + 2) Cycloaddition Reaction

Page 4: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

Scope with Respect to the Alkyne Component

Page 5: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

Phenols Equipped with Different Substituents

Page 6: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

Proposed Mechanistic Cycle

Page 7: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

(4 + 3) Annulations

benzamide furan-2-carboxamide

spiro dihydroisoquinolinone furan-fused azepinone

Page 8: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

Proposed mechanism

Page 9: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

(4 + 3) Annulations

vinylcarbenoids

Page 10: Rhodium-Catalyzed C−H Functionalizationweb.pkusz.edu.cn/zhaogroup/files/2013/05/Rhodium... · C—H Activation Mild Rhodium(III)-Catalyzed Cyclization of Amides with CL,ß- Unsaturated

(4 + 3) Annulations Angew. Chem. Int. Ed. 2013, 52, 5393 –5397

FeCl3-Catalyzed Cyclization of -Sulfonamido-Allenes · PDF fileS1 FeCl3-Catalyzed Cyclization of -Sulfonamido-Allenes with Aldehydes-The Substituent Effect Jiajia Cheng, Xinjun Tang,

Rhodium Catalyzed C–H Bond Functionalization ...digitalassets.lib.berkeley.edu/etd/ucb/text/Tsai_berkeley_0028E... · Rhodium Catalyzed C-H Bond Functionalization: Development of

Pd-Catalyzed Borylative Cyclization Reactions of

Accepted Manuscript - webdelprofesor.ula.vewebdelprofesor.ula.ve/ciencias/ricardo/PDF/Rhodium... · Accepted Manuscript Title: Rhodium catalyzed hydroformylation of monoterpenes containing

Rhodium(III)-catalyzed chelation-assisted C-H imidation of ...xingweili.snnu.edu.cn/__local/B/17/BB/4E1F1C44DD012A6DCFAEAA1… · Rhodium(III)-catalyzed chelation-assisted C−H imidation

Rhodium( I)- and Iridium( 1)-Catalyzed Hydroboration Reactions

conrotatory Metal Catalyzed Cyclization … · conrotatory Metal Catalyzed Cyclization oof pEenynesning? ... A. Fürstner, N. Chatani, M. Malacria, A. S. K. Hashmi, F. D. Toste, F

PGM-Catalyzed Cyclization Reactions for the Synthesis of Ergot …ccc.chem.pitt.edu/wipf/Current Literature/Austin_2.pdf · 2017-11-20 · PGM-Catalyzed Cyclization Reactions for

Rhodium catalyzed hydroformylation - CH 02

Rhodium-Catalyzed Intermolecular Hydroacylation …...ii Rhodium-Catalyzed Intermolecular Hydroacylation of Unactivated Alkenes and Application to the Total Synthesis of Octaketide

Rhodium catalyzed hydroformylation - CH 08

Rhodium catalyzed hydroformylation - CH 05

Rhodium trichloride catalyzed hydroboration of 1-octene

Rhodium-Catalyzed Hydroformylation of Alkynes Employing a ... · Rhodium-Catalyzed Hydroformylation of Alkynes Employing a Self-Assembling Ligand System Vladislav Agabekov, Wolfgang

Rhodium-Catalyzed Hydroboration: Directed Asymmetric

A General, Rhodium‐Catalyzed, Synthesis of Deuterated

Rh-catalyzed aerobic oxidative cyclization of anilines

Coupling Rhodium‐Catalyzed Hydroformylation of 10

Phosphazene-Catalyzed Intramolecular Cyclization of ... · PDF filePhosphazene-Catalyzed Intramolecular Cyclization of Nitrogen-Tethered ... (21.1 mg, 0 .03 mmol) and CuI (5 ... 2939,

University of Groningen Rhodium-Catalyzed Asymmetric ...Monodentate Phosphoramidites as Ligands in the Rhodium-catalyzed Asymmetric Hydrogenation of Aromatic Enamides 115 4.2.1.2 Synthesis

Synthesis of various substituted naphthalene via Palladium catalyzed Cyclization

Rhodium-Catalyzed Direct C-H Functionalizations of ...Rhodium-Catalyzed Direct C-H Functionalizations of Sulfoximines and Copper-Catalyzed Enantioselective Synthesis of Dihydropyrazoles

Rhodium(III)-catalyzed synthesis of indanones via C–H

Rhodium catalyzed hydroformylation - CH 01

Substrate Activation Strategies in Rhodium(III)-Catalyzed ...xingweili.snnu.edu.cn/__local/F/3D/31/D0D938414CD6ABD0AFB6A9C… · Substrate Activation Strategies in Rhodium(III)-Catalyzed

Tandem cyclization–cycloaddition reactions of …repository.ias.ac.in/28928/1/309.pdf · Tandem cyclization–cycloaddition reactions of rhodium generated carbenoids from a-diazo

University of Groningen Rhodium-Catalyzed Asymmetric

Rhodium catalyzed synthesis of difluoromethyl cyclopropanes

Rhodium(III)-Catalyzed Difunctionalization of Alkenes

Rhodium Catalyzed Hydroacylation: Synthesis of ...Rhodium(I) catalyzed hydroacylation has been used to form cyclopentanones from unsaturated aldehydes, but has had limited success

Rhodium catalyzed hydroformylation - CH 06

Rhodium catalyzed hydroformylation - CH 04

Investigations on rhodium-catalyzed asymmetric ... · Catalytic cycle for the branched selective hydroformylation of a terminal linear alkene. Rhodium catalyzed hydroformylation however

Rhodium-Catalyzed Intra- and Intermolecular Alkene

Remarkably Facile Borane-Promoted, Rhodium-Catalyzed ... · Remarkably Facile Borane-Promoted, Rhodium-Catalyzed Asymmetric Hydrogenation of Tri ... were prepared, albeit with a major