Cyclic (Alkyl)(amino)carbenes: Synthesis of Iminium Precursors and Structural Properties

Vermersch, François; Oliveira, Luana; Hunter, Joseph; Soleilhavoup, Michele; Jazzar, Rodolphe; Bertrand, Guy

doi:10.1021/acs.joc.1c03075

Title: Cyclic (Alkyl)(amino)carbenes: Synthesis of Iminium Precursors and Structural Properties

Journal Article · 07 February 2022 · Journal of Organic Chemistry

DOI: https://doi.org/10.1021/acs.joc.1c03075 · OSTI ID:1905846

^[1]; Oliveira, Luana ^[2]; Hunter, Joseph ^[2];

^[2];

^[2]

Univ. of California, San Diego, CA (United States). UCSD-CNRS Joint Research Lab.; UCSD
Univ. of California, San Diego, CA (United States). UCSD-CNRS Joint Research Lab.

Using readily available pre-allylated aldehydes, in this work we report a simple and divergent synthesis of cyclic (alkyl)(amino)carbene (CAAC) iminium precursors. Using a combination of crystallographic data and steric maps, we further elaborate on the specific steric properties of CAAC ligands with respect to state-of-the-art phosphine and carbene ligands.

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Research Organization:: Univ. of California, San Diego, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); French National Research Agency (ANR)

Grant/Contract Number:: SC0009376

OSTI ID:: 1905846

Journal Information:: Journal of Organic Chemistry, Journal Name: Journal of Organic Chemistry Journal Issue: 5 Vol. 87; ISSN 0022-3263

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Stable Cyclic (Alkyl)(Amino)Carbenes as Rigid or Flexible, Bulky, Electron-Rich Ligands for Transition-Metal Catalysts: A Quaternary Carbon Atom Makes the Difference Lavallo, Vincent; Canac, Yves; Präsang, Carsten Angewandte Chemie International Edition, Vol. 44, Issue 35, p. 5705-5709 https://doi.org/10.1002/anie.200501841	journal	September 2005
A Rigid Cyclic (Alkyl)(amino)carbene Ligand Leads to Isolation of Low-Coordinate Transition-Metal Complexes Lavallo, Vincent; Canac, Yves; DeHope, Alan Angewandte Chemie International Edition, Vol. 44, Issue 44 https://doi.org/10.1002/anie.200502566	journal	November 2005
Intramolecular “Hydroiminiumation” of Alkenes: Application to the Synthesis of Conjugate Acids of Cyclic Alkyl Amino Carbenes (CAACs) Jazzar, Rodolphe; Dewhurst, Rian D.; Bourg, Jean-Baptiste Angewandte Chemie International Edition, Vol. 46, Issue 16 https://doi.org/10.1002/anie.200605083	journal	April 2007
Biaryl Phosphane Ligands in Palladium-Catalyzed Amination Surry, David S.; Buchwald, Stephen L. Angewandte Chemie International Edition, Vol. 47, Issue 34 https://doi.org/10.1002/anie.200800497	journal	August 2008
Stable Cyclic Carbenes and Related Species beyond Diaminocarbenes Melaimi, Mohand; Soleilhavoup, Michèle; Bertrand, Guy Angewandte Chemie International Edition, Vol. 49, Issue 47 https://doi.org/10.1002/anie.201000165	journal	September 2010
Activation of SiH, BH, and PH Bonds at a Single Nonmetal Center Frey, Guido D.; Masuda, Jason D.; Donnadieu, Bruno Angewandte Chemie International Edition, Vol. 49, Issue 49 https://doi.org/10.1002/anie.201005698	journal	October 2010
Copper and Silver Carbene Complexes without Heteroatom-Stabilization: Structure, Spectroscopy, and Relativistic Effects Hussong, Matthias W.; Hoffmeister, Wilhelm T.; Rominger, Frank Angewandte Chemie International Edition, Vol. 54, Issue 35 https://doi.org/10.1002/anie.201504117	journal	July 2015
Cyclic (Alkyl)(amino)carbenes (CAACs): Recent Developments Melaimi, Mohand; Jazzar, Rodolphe; Soleilhavoup, Michèle Angewandte Chemie International Edition, Vol. 56, Issue 34 https://doi.org/10.1002/anie.201702148	journal	June 2017
Readily Available Primary Aminoboranes as Powerful Reagents for Aldimine Synthesis Junor, Glen P.; Romero, Erik A.; Chen, Xi Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201814081	journal	February 2019
cAAC‐Stabilized 9,10‐diboraanthracenes—Acenes with Open‐Shell Singlet Biradical Ground States Saalfrank, Christian; Fantuzzi, Felipe; Kupfer, Thomas Angewandte Chemie International Edition, Vol. 59, Issue 43 https://doi.org/10.1002/anie.202008206	journal	August 2020
Highly Colored Boron‐Doped Thiazolothiazoles from the Reductive Dimerization of Boron Isothiocyanates Hagspiel, Stephan; Arrowsmith, Merle; Fantuzzi, Felipe Angewandte Chemie International Edition, Vol. 60, Issue 12 https://doi.org/10.1002/anie.202015508	journal	February 2021
Cyclic (Alkyl)(amino)carbene Ligands Enable Cu‐Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes** Gao, Yang; Yazdani, Sima; Kendrick, Aaron Angewandte Chemie International Edition, Vol. 60, Issue 36 https://doi.org/10.1002/anie.202106107	journal	July 2021
Carbene‐Stabilized Dithiolene (L ⁰ ) Zwitterions Wang, Yuzhong; Tran, Phuong M.; Xie, Yaoming Angewandte Chemie International Edition, Vol. 60, Issue 42 https://doi.org/10.1002/anie.202108498	journal	September 2021
Adduct Formation, B−H Activation and Ring Expansion at Room Temperature from Reactions of HBcat with NHCs Würtemberger-Pietsch, Sabrina; Schneider, Heidi; Marder, Todd B. Chemistry - A European Journal, Vol. 22, Issue 37 https://doi.org/10.1002/chem.201603328	journal	August 2016
Twisting versus Delocalization in CAAC‐ and NHC‐Stabilized Boron‐Based Biradicals: The Roles of Sterics and Electronics Schmid, Paul; Fantuzzi, Felipe; Klopf, Jonas Chemistry – A European Journal, Vol. 27, Issue 16 https://doi.org/10.1002/chem.202004619	journal	January 2021
Samb V ca: A Web Application for the Calculation of the Buried Volume of N-Heterocyclic Carbene Ligands Poater, Albert; Cosenza, Biagio; Correa, Andrea European Journal of Inorganic Chemistry, Vol. 2009, Issue 13 https://doi.org/10.1002/ejic.200801160	journal	May 2009
What Wanzlick Did Not Dare To Dream: Cyclic (Alkyl)(amino)carbenes (cAACs) as New Key Players in Transition-Metal Chemistry: What Wanzlick Did Not Dare To Dream: Cyclic (Alkyl)(amino)carbenes (cAACs) as New Key Players in Transition-Metal Chemistry Paul, Ursula S. D.; Radius, Udo European Journal of Inorganic Chemistry, Vol. 2017, Issue 28 https://doi.org/10.1002/ejic.201700397	journal	July 2017
CAACs as efficient ancillary ligands for the synthesis of robust catalysts Singh, Rahul Kumar; Khan, Tamanna K.; Misra, Shilpi Journal of Organometallic Chemistry, Vol. 956 https://doi.org/10.1016/j.jorganchem.2021.122133	journal	December 2021
Intermolecular reductive coupling of hindered N-aryl imines towards the modular synthesis of chiral N-heterocyclic carbenes Mercer, Gregory J.; Sturdy, Megan; Jensen, David R. Tetrahedron, Vol. 61, Issue 26 https://doi.org/10.1016/j.tet.2005.03.124	journal	June 2005
Biaryl monophosphine ligands in palladium-catalyzed C–N coupling: An updated User's guide Ingoglia, Bryan T.; Wagen, Corin C.; Buchwald, Stephen L. Tetrahedron, Vol. 75, Issue 32 https://doi.org/10.1016/j.tet.2019.05.003	journal	August 2019
Cyclic Alkyl(amino) Carbene Stabilized Complexes with Low Coordinate Metals of Enduring Nature Roy, Sudipta; Mondal, Kartik Chandra; Roesky, Herbert W. Accounts of Chemical Research, Vol. 49, Issue 3 https://doi.org/10.1021/acs.accounts.5b00381	journal	February 2016
Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications Jazzar, Rodolphe; Soleilhavoup, Michele; Bertrand, Guy Chemical Reviews, Vol. 120, Issue 9 https://doi.org/10.1021/acs.chemrev.0c00043	journal	April 2020
SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps Falivene, Laura; Credendino, Raffaele; Poater, Albert Organometallics, Vol. 35, Issue 13 https://doi.org/10.1021/acs.organomet.6b00371	journal	June 2016
Influence of Carbene and Phosphine Ligands on the Catalytic Activity of Gold Complexes in the Hydroamination and Hydrohydrazination of Alkynes Yazdani, Sima; Junor, Glen P.; Peltier, Jesse L. ACS Catalysis, Vol. 10, Issue 9 https://doi.org/10.1021/acscatal.0c01352	journal	March 2020
Reversibly Photoswitchable Catalysts for Olefin Metathesis Reactions Park, Seongwook; Byun, Seunghwan; Ryu, Huijeoung ACS Catalysis, Vol. 11, Issue 22 https://doi.org/10.1021/acscatal.1c04281	journal	November 2021
Cyclic (Alkyl)(Amino)Carbenes (CAACs): Stable Carbenes on the Rise Soleilhavoup, Michèle; Bertrand, Guy Accounts of Chemical Research, Vol. 48, Issue 2 https://doi.org/10.1021/ar5003494	journal	December 2014
Realizing Metal-Free Carbene-Catalyzed Carbonylation Reactions with CO Peltier, Jesse L.; Tomás-Mendivil, Eder; Tolentino, Daniel R. Journal of the American Chemical Society, Vol. 142, Issue 43 https://doi.org/10.1021/jacs.0c09938	journal	October 2020
Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds Chen, Liye; Ren, Peng; Carrow, Brad P. Journal of the American Chemical Society, Vol. 138, Issue 20 https://doi.org/10.1021/jacs.6b03215	journal	May 2016
Reactions of Persistent Carbenes with Hydrogen-Terminated Silicon Surfaces Zhukhovitskiy, Aleksandr V.; Mavros, Michael G.; Queeney, K. T. Journal of the American Chemical Society, Vol. 138, Issue 27 https://doi.org/10.1021/jacs.6b04962	journal	June 2016
Synthesis of Hemilabile Cyclic (Alkyl)(amino)carbenes (CAACs) and Applications in Organometallic Chemistry Chu, Jiaxiang; Munz, Dominik; Jazzar, Rodolphe Journal of the American Chemical Society, Vol. 138, Issue 25 https://doi.org/10.1021/jacs.6b05221	journal	June 2016
Bicyclic (Alkyl)(amino)carbenes (BICAACs): Stable Carbenes More Ambiphilic than CAACs Tomás-Mendivil, Eder; Hansmann, Max M.; Weinstein, Cory M. Journal of the American Chemical Society, Vol. 139, Issue 23 https://doi.org/10.1021/jacs.7b04640	journal	June 2017
Highly Ambiphilic Room Temperature Stable Six-Membered Cyclic (Alkyl)(amino)carbenes Weinstein, Cory M.; Junor, Glen P.; Tolentino, Daniel R. Journal of the American Chemical Society, Vol. 140, Issue 29 https://doi.org/10.1021/jacs.8b05518	journal	June 2018
Reductive Elimination at Carbon under Steric Control Tolentino, Daniel R.; Neale, Samuel E.; Isaac, Connie J. Journal of the American Chemical Society, Vol. 141, Issue 25 https://doi.org/10.1021/jacs.9b04957	journal	June 2019
Electronic and Steric Control in Regioselective Addition Reactions of Organolithium Reagents with Enaldimines Tomioka, Kiyoshi; Shioya, Yoshito; Nagaoka, Yasuo The Journal of Organic Chemistry, Vol. 66, Issue 21 https://doi.org/10.1021/jo015766b	journal	September 2001
Intramolecular “Hydroiminiumation and -amidiniumation” of Alkenes: A Convenient, Flexible, and Scalable Route to Cyclic Iminium and Imidazolinium Salts Jazzar, Rodolphe; Bourg, Jean-Baptiste; Dewhurst, Rian D. The Journal of Organic Chemistry, Vol. 72, Issue 9 https://doi.org/10.1021/jo0703909	journal	April 2007
A Combined Experimental and Theoretical Study Examining the Binding of N -Heterocyclic Carbenes (NHC) to the CpRuCl (Cp = η ⁵ -C ₅ Me ₅ ) Moiety: Insight into Stereoelectronic Differences between Unsaturated and Saturated NHC Ligands Hillier, Anna C.; Sommer, William J.; Yong, Ben S. Organometallics, Vol. 22, Issue 21 https://doi.org/10.1021/om034016k	journal	October 2003
Towards the online computer-aided design of catalytic pockets Falivene, Laura; Cao, Zhen; Petta, Andrea Nature Chemistry, Vol. 11, Issue 10 https://doi.org/10.1038/s41557-019-0319-5	journal	September 2019
Recent advances in the chemistry and applications of N-heterocyclic carbenes Bellotti, Peter; Koy, Maximilian; Hopkinson, Matthew N. Nature Reviews Chemistry, Vol. 5, Issue 10 https://doi.org/10.1038/s41570-021-00321-1	journal	September 2021
IPr* an easily accessible highly hindered N-heterocyclic carbene Berthon-Gelloz, Guillaume; Siegler, Maxime A.; Spek, Anthony L. Dalton Trans., Vol. 39, Issue 6 https://doi.org/10.1039/B921894G	journal	January 2010
The use of the sterically demanding IPr* and related ligands in catalysis Izquierdo, Frédéric; Manzini, Simone; Nolan, Steven P. Chem. Commun., Vol. 50, Issue 95 https://doi.org/10.1039/C4CC05289G	journal	January 2014
Stable cyclic (alkyl)(amino)carbene (cAAC) radicals with main group substituents Kundu, Subrata; Sinhababu, Soumen; Chandrasekhar, Vadapalli Chemical Science, Vol. 10, Issue 18 https://doi.org/10.1039/C9SC01351B	journal	January 2019
The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis Pichon, Delphine; Soleilhavoup, Michele; Morvan, Jennifer Chemical Science, Vol. 10, Issue 33 https://doi.org/10.1039/C9SC02810B	journal	January 2019
Tethered CAAC–CAAC dimers: oxidation to persistent radical cations and bridging-unit dependent reactivity/stability of the dications Nayak, Mithilesh Kumar; Suhr, Simon; Chrysochos, Nicolas Chemical Communications, Vol. 57, Issue 10 https://doi.org/10.1039/D0CC07385G	journal	January 2021
Percent buried volume for phosphine and N-heterocyclic carbene ligands: steric properties in organometallic chemistry Clavier, Hervé; Nolan, Steven P. Chemical Communications, Vol. 46, Issue 6 https://doi.org/10.1039/b922984a	journal	January 2010
Facile Splitting of Hydrogen and Ammonia by Nucleophilic Activation at a Single Carbon Center Frey, G. D.; Lavallo, V.; Donnadieu, B. Science, Vol. 316, Issue 5823 https://doi.org/10.1126/science.1141474	journal	April 2007
Synthesis of an extremely sterically shielding N-heterocyclic carbene ligand Weber, Simone G.; Loos, Christian; Rominger, Frank Arkivoc, Vol. 2012, Issue 3 https://doi.org/10.3998/ark.5550190.0013.317	journal	January 2012

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Aldehydes
Granular materials
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Nuclear magnetic resonance spectroscopy

CCDC 2127092: Experimental Crystal Structure Determination François, Vermersch,; Luana, Oliveira,; Joseph, Hunter, https://doi.org/10.5517/ccdc.csd.cc29ddw0 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2127093: Experimental Crystal Structure Determination François, Vermersch,; Luana, Oliveira,; Joseph, Hunter, https://doi.org/10.5517/ccdc.csd.cc29ddx1 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2127094: Experimental Crystal Structure Determination François, Vermersch,; Luana, Oliveira,; Joseph, Hunter, https://doi.org/10.5517/ccdc.csd.cc29ddy2 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2127095: Experimental Crystal Structure Determination François, Vermersch,; Luana, Oliveira,; Joseph, Hunter, https://doi.org/10.5517/ccdc.csd.cc29ddz3 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2127096: Experimental Crystal Structure Determination François, Vermersch,; Luana, Oliveira,; Joseph, Hunter, https://doi.org/10.5517/ccdc.csd.cc29df05 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2127097: Experimental Crystal Structure Determination François, Vermersch,; Luana, Oliveira,; Joseph, Hunter, https://doi.org/10.5517/ccdc.csd.cc29df16 The current record is supplemented by this dataset	dataset	January 2022

Title: Cyclic (Alkyl)(amino)carbenes: Synthesis of Iminium Precursors and Structural Properties

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