Online citations, reference lists, and bibliographies.

Substituent Enabled Divergent Synthesis Of N-Heterocycles: A Metal Carbene Approach Involving Intramolecular Carbene Interception

Hua-Dong Xu, Ke Xu, Zhi‐Hong Jia, H. Zhou, P. Jiang, Xiao-long Lu, Ying-Peng Pan, H. Wu, Y. Ding, Mei-Hua Shen, Xian‐Hua Pan
Published 2014 · Chemistry

Cite This
Download PDF
Analyze on Scholarcy
Share
N-Aryl-N-allyl-bis-functionalized amino-1-sulfonyl-1,2,3-trizoles undergo rhodium-catalyzed cyclization reactions and subsequent hydrolytic cleavage of the sulfonyl imine to give two structurally distinct N-heterocycles, 3-indolyl aldehydes and 3-azabicyclo[3,1,0]hexyl aldehydes. The product ratio can be tuned by varying the electronic properties of the two functional groups attached to the N atom. Based on these findings, two efficient and general methods for the synthesis of highly valuable 3-indolyl aldehydes and 3-azabicyclo[3,1,0]hexyl aldehydes have been developed.
This paper references
10.1021/CR020033S
The combinatorial synthesis of bicyclic privileged structures or privileged substructures.
D. A. Horton (2003)
10.1002/anie.201400881
Rhodium(II)-catalyzed intramolecular annulation of 1-sulfonyl-1,2,3-triazoles with pyrrole and indole rings: facile synthesis of N-bridgehead azepine skeletons.
J. Yang (2014)
10.1021/JA074729K
Highly enantioselective insertion of carbenoids into O-H bonds of phenols: an efficient approach to chiral alpha-aryloxycarboxylic esters.
C. Chen (2007)
10.1126/science.1210735
High-Throughput Discovery of New Chemical Reactions
J. Montgomery (2011)
10.1002/EJOC.201100150
Transition Metal-Catalyzed Formation of N-Heterocycles via Aryl- or Vinyl C–H Bond Amination
B. J. Stokes (2011)
10.1002/ANGE.201209338
Rhodiumiminocarbene aus N-Sulfonyltriazolen: vielseitig abstimmbare Reaktivität†
Anton V. Gulevich (2013)
10.1021/ja400350c
Transannulation of 1-sulfonyl-1,2,3-triazoles with heterocumulenes.
S. Chuprakov (2013)
10.1021/CR010007E
Stereoselective cyclopropanation reactions.
H. Lebel (2003)
10.1021/ja4025337
Catalytic asymmetric synthesis of pyrroloindolines via a rhodium(II)-catalyzed annulation of indoles.
J. Spangler (2013)
10.1021/ja504797x
Role of sterically demanding chiral dirhodium catalysts in site-selective C-H functionalization of activated primary C-H bonds.
Changming Qin (2014)
10.1021/ja503163k
Highly site-selective direct C-H bond functionalization of phenols with α-aryl-α-diazoacetates and diazooxindoles via gold catalysis.
Zhunzhun Yu (2014)
10.1021/ol500309x
Rhodium(II)-catalyzed stereocontrolled synthesis of dihydrofuran-3-imines from 1-tosyl-1,2,3-triazoles.
Alistair Boyer (2014)
10.1021/ja00072a021
Ligand effects on dirhodium(II) carbene reactivities. Highly effective switching between competitive carbenoid transformations
A. Padwa (1993)
Bicifadine nonopioid analgesic : USAN norepinephrine transporter inhibitor serotonin transporter inhibitor NMDA antagonist
L. Sorbera (2005)
10.1021/ol501618z
Synthesis of substituted 3-indolylimines and indole-3-carboxaldehydes by rhodium(II)-catalyzed annulation.
Basker Rajagopal (2014)
10.1126/SCIENCE.287.5460.1964
Target-oriented and diversity-oriented organic synthesis in drug discovery.
S. Schreiber (2000)
10.1021/ja412663a
Intramolecular dearomatizing [3 + 2] annulation of α-imino carbenoids with aryl rings furnishing 3,4-fused indole skeletons.
T. Miura (2014)
10.1021/ol5002347
Preparation of triazoloindoles via tandem copper catalysis and their utility as α-imino rhodium carbene precursors.
Yanpeng Xing (2014)
10.1021/JA0660195
Rh-Catalyzed Intermolecular Reactions of Alkynes with α-Diazoesters That Possess β-Hydrogens: Ligand-Based Control over Divergent Pathways
Patricia Panne (2007)
10.1021/ol4007629
Synthesis of 3-aza-bicyclo[3.1.0]hexan-2-one derivatives via gold-catalyzed oxidative cyclopropanation of N-allylynamides.
K. Wang (2013)
10.1021/ja311392m
Highly selective catalyst-dependent competitive 1,2-C→C, -O→C, and -N→C migrations from β-methylene-β-silyloxy-β-amido-α-diazoacetates.
Xichen Xu (2013)
10.1021/ja502229c
Enantioselective insertion of a carbenoid carbon into a C-C bond to expand cyclobutanols to cyclopentanols.
A. Yada (2014)
10.1126/science.1207922
A Simple, Multidimensional Approach to High-Throughput Discovery of Catalytic Reactions
Daniel W. Robbins (2011)
10.1021/ar300101k
Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.
Q. Xiao (2013)
10.1021/jm00137a002
1-Aryl-3-azabicyclo[3.1.0]hexanes, a new series of nonnarcotic analgesic agents
J. W. Epstein (1981)
10.1021/cr900211p
Marine indole alkaloids: potential new drug leads for the control of depression and anxiety.
Anna J Kochanowska-Karamyan (2010)
10.1021/ja805079v
Rhodium-catalyzed transannulation of 1,2,3-triazoles with nitriles.
Tony Horneff (2008)
10.1038/nchem.1406
Highly enantioselective trapping of zwitterionic intermediates by imines
H. Qiu (2012)
10.1021/ol4027655
Intramolecular transannulation of alkynyl triazoles via alkyne-carbene metathesis step: access to fused pyrroles.
Y. Shi (2013)
10.1002/anie.201309650
Rhodium(III)-catalyzed ortho alkenylation of N-phenoxyacetamides with N-tosylhydrazones or diazoesters through C-H activation.
Fangdong Hu (2014)
10.1016/j.cbpa.2010.02.018
Privileged scaffolds for library design and drug discovery.
Matthew E. Welsch (2010)
10.1021/JM030267J
Characteristic physical properties and structural fragments of marketed oral drugs.
M. Vieth (2004)
10.1021/ar300051u
Transition-metal-catalyzed enantioselective heteroatom-hydrogen bond insertion reactions.
S. Zhu (2012)
10.1021/ar5000055
The [3 + 3]-Cycloaddition Alternative for Heterocycle Syntheses: Catalytically Generated Metalloenolcarbenes as Dipolar Adducts
Xinfang Xu (2014)
10.1021/ja408185c
Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes.
S. Chuprakov (2014)
10.1002/anie.201209338
Versatile reactivity of rhodium-iminocarbenes derived from N-sulfonyl triazoles.
A. Gulevich (2013)
10.1039/c2cc34609e
Ring expansion of alkynyl cyclopropanes to highly substituted cyclobutenes via a N-sulfonyl-1,2,3-triazole intermediate.
Renhe Liu (2013)
10.1007/s10593-013-1317-y
Recent advances in the cyclization of N-heterocycles: the role of enabling techniques (review)
G. Cravotto (2013)
10.1002/ANIE.201306706
Catalytic asymmetric transannulation of NH-1,2,3-triazoles with olefins.
S. W. Kwok (2014)
10.1002/ANGE.201104807
Übergangsmetallkatalysierte denitrogenierende Transanellierungen: Umwandlung von Triazolen in andere heterocyclische Systeme
Buddhadeb Chattopadhyay (2012)
10.1021/JA3061529
Scope and mechanistic analysis of the enantioselective synthesis of allenes by rhodium-catalyzed tandem ylide formation/[2,3]-sigmatropic rearrangement between donor/acceptor carbenoids and propargylic alcohols.
Zhanjie Li (2012)
10.1002/anie.201206388
Sulfonyl-1,2,3-triazoles: convenient synthones for heterocyclic compounds.
M. Zibinsky (2013)
10.1002/ange.200390315
Buchbesprechung: Lorenz Oken (1779–1851). Ein politischer Naturphilosoph Herausgegeben von Olaf Breidbach, Hans‐Joachim Fliedner und Klaus Ries
Christoph Meinel (2003)
10.1021/CR950022H
Cascade Processes of Metallo Carbenoids.
A. Padwa (1996)
10.1002/ANIE.200390343
Book Review: Carbene Chemistry Edited by Guy Bertrand
W. Kirmse (2003)
10.1021/CS4006666
Catalytic Cascade Reactions Involving Metal Carbene Migratory Insertion
Ying Pei Xia (2013)
10.1039/C2SC21185H
Indole synthesis – something old, something new
M. Inman (2013)
10.1021/ja500118w
Formal carbene insertion into C-C bond: Rh(I)-catalyzed reaction of benzocyclobutenols with diazoesters.
Ying Xia (2014)
10.1002/ANGE.201309650
Rhodium(III)-CatalyzedorthoAlkenylation ofN-Phenoxyacetamides withN-Tosylhydrazones or Diazoesters through CH Activation
Fangdong Hu (2014)
10.1021/ja3099728
Stereoselective Rh2(S-IBAZ)4-catalyzed cyclopropanation of alkenes, alkynes, and allenes: asymmetric synthesis of diacceptor cyclopropylphosphonates and alkylidenecyclopropanes.
V. Lindsay (2013)
10.1021/ja801755z
Cooperative catalysis with chiral Brønsted acid-Rh2(OAc)4: highly enantioselective three-component reactions of diazo compounds with alcohols and imines.
Wenhao Hu (2008)
10.1039/B000708K
Catalytic enantioselective rearrangements and cycloadditions involving ylides from diazo compounds
D. Hodgson (2001)
10.1038/nchem.651
Enantioselective iron-catalysed O–H bond insertions
S. Zhu (2010)
10.1002/anie.201104807
Transition-metal-catalyzed denitrogenative transannulation: converting triazoles into other heterocyclic systems.
Buddhadeb Chattopadhyay (2012)
10.1002/ANGE.200703016
Enantioselektive Insertion von Metallcarbenen in N‐H‐Bindungen: ein potenziell vielseitiger Weg zu chiralen Aminderivaten
C. Moody (2007)
10.1021/ja401610p
α-Diazo-β-ketonitriles: uniquely reactive substrates for arene and alkene cyclopropanation.
Roger R. Nani (2013)
10.1021/JA074483J
Copper-Catalyzed Asymmetric N−H Insertion Reactions: Couplings of Diazo Compounds with Carbamates to Generate α-Amino Acids
E. C. Lee (2007)
10.1021/ja4047069
Generation of rhodium(I) carbenes from ynamides and their reactions with alkynes and alkenes.
Renhe Liu (2013)
10.1126/science.1213920
Discovery of an α-Amino C–H Arylation Reaction Using the Strategy of Accelerated Serendipity
Andrew McNally (2011)
10.1002/ANIE.200703016
Enantioselective insertion of metal carbenes into N-H bonds: a potentially versatile route to chiral amine derivatives.
C. Moody (2007)
10.1021/ja401386z
Rhodium-catalyzed conversion of furans to highly functionalized pyrroles.
Brendan T. Parr (2013)
10.1021/ja500382c
Copper-mediated oxidative transformation of N-allyl enamine carboxylates toward synthesis of azaheterocycles.
K. K. Toh (2014)
10.1021/ja408306a
Copper-catalyzed B-H bond insertion reaction: a highly efficient and enantioselective C-B bond-forming reaction with amine-borane and phosphine-borane adducts.
Qing-Qing Cheng (2013)
10.1021/ar400181x
A Non-Diazo Approach to α-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation
L. Zhang (2014)
10.1021/ja407166r
Stereoselective synthesis of 2,3-dihydropyrroles from terminal alkynes, azides, and α,β-unsaturated aldehydes via N-sulfonyl-1,2,3-triazoles.
T. Miura (2013)
10.1021/ja00031a048
Control of chemoselectivity in catalytic carbenoid reactions. Dirhodium(II) ligand effects on relative reactivities
A. Padwa (1992)
10.1021/ar300340k
Novel multicomponent reactions via trapping of protic onium ylides with electrophiles.
Xin Guo (2013)



This paper is referenced by
10.1016/J.CCR.2015.09.012
The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014
James W. Herndon (2016)
10.1002/anie.202000859
Asymmetric Reductive and Alkynylative Heck Bicyclization of Enynes to Access Conformationally Restricted Aza[3.1.0]bicycles.
Jianrong Steve Zhou (2020)
10.1002/CHIN.201517156
Substituent Enabled Divergent Synthesis of N‐Heterocycles: A Metal Carbene Approach Involving Intramolecular Carbene Interception.
Hua-Dong Xu (2015)
10.1016/J.TETLET.2015.10.059
A one-pot construction of acridones by rhodium catalyzed reaction of N-phenyl-2-(1-sulfonyl-1H-1,2,3-triazol-4-yl)aniline
Hua-Dong Xu (2015)
10.1016/J.TET.2015.11.021
Synthesis of 2,5-epoxy-1,4-benzoxazepines via rhodium(II)-catalyzed reaction of 1-tosyl-1,2,3-triazoles and salicylaldehydes
Jiang Ying Meng (2016)
10.1016/J.TET.2015.05.113
Expedient catalytic construction of azabicyclo[4.1.0]/[5.1.0] carbaldehydes via intramolecular cyclopropanation
Xian‐Hua Pan (2015)
10.1021/ol503247t
One-pot protocol to functionalized benzopyrrolizidine catalyzed successively by Rh2(OAc)4 and Cu(OTf)2: a transition metal-Lewis acid catalysis relay.
Hua-Dong Xu (2015)
10.1002/EJOC.201801103
Divergent Palladium‐ and Platinum‐Catalyzed Intramolecular Hydroamination/Hydroarylation of O‐Propargyl‐2‐aminophenols
Michael S Christodoulou (2018)
10.1002/chem.201800689
The Expanding Utility of Rhodium-Iminocarbenes: Recent Advances in the Synthesis of Natural Products and Related Scaffolds.
Yun Li (2018)
10.1021/acs.orglett.5b02798
Stereoselective Construction of Bridged trans-aza-Bicyclo[7/6,3/2,1]alkenyl Imines through Ring Expansion aza-Cope Rearrangement.
Mei-Hua Shen (2015)
10.1039/C6QO00084C
Straightforward regioselective construction of 3,4-dihydro-2H-1,4-thiazine by rhodium catalysed [3 + 3] cycloaddition of thiirane with 1-sulfonyl-1,2,3-triazole: a pronounced acid additive effect
Xiao-long Lu (2016)
10.1039/c5ob00085h
An efficient approach to 1,2,3-trisubstituted indole via rhodium catalyzed carbene C(sp(3))-H bond insertion.
Mei-Hua Shen (2015)
Semantic Scholar Logo Some data provided by SemanticScholar