Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP

Su, Jessica K.; Jin, Zexin; Zhang, Rui; Lu, Gang; Liu, Peng; Xia, Yan

doi:10.1002/ange.201909688

Title: Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP

Journal Article · 22 October 2019 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201909688 · OSTI ID:1571332

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^[1]; Zhang, Rui ^[2]; Lu, Gang ^[2];

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Department of Chemistry Stanford University Stanford CA 94305 USA
Department of Chemistry University of Pittsburgh Pittsburgh PA 15260 USA

Abstract Ring‐opening metathesis polymerization (ROMP) has become one of the most important living polymerizations. Cyclopropenes (CPEs) remain underexplored for ROMP. Described here is that the simple swap of 1‐methyl to 1‐phenyl on 1‐(benzoyloxymethyl)CPEs elicited strikingly different modes of reactivity, switching from living polymerization to either selective single‐addition or living alternating ROMP. The distinct reactivity stems from differences in steric repulsions at the Ru alkylidene after CPE ring opening. Possible olefin or oxygen chelation from ring‐opened CPE substituents was also observed to significantly affect the rate of propagation. These results demonstrate the versatility of CPEs as a new class of monomers for ROMP, provide mechanistic insights for designing new monomers with rare single‐addition reactivity, and generate a new functionalizable alternating copolymer scaffold with controlled molecular weight and low dispersity.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1571332

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 49 Vol. 131; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (57)

Synthesis of A,B-Alternating Copolymers by Ring-Opening-Insertion-Metathesis Polymerization Choi, Tae-Lim; Rutenberg, Isaac M.; Grubbs, Robert H. Angewandte Chemie, Vol. 114, Issue 20 https://doi.org/10.1002/1521-3757(20021018)114:20<3995::AID-ANGE3995>3.0.CO;2-Z	journal	October 2002
Mechanism of Olefin Metathesis with Catalysis by Ruthenium Carbene Complexes: Density Functional Studies on Model Systems Vyboishchikov, Sergei F.; Bühl, Michael; Thiel, Walter Chemistry - A European Journal, Vol. 8, Issue 17 https://doi.org/10.1002/1521-3765(20020902)8:17<3962::AID-CHEM3962>3.0.CO;2-X	journal	September 2002
Synthesis of A,B-Alternating Copolymers by Ring-Opening-Insertion-Metathesis Polymerization Choi, Tae-Lim; Rutenberg, Isaac M.; Grubbs, Robert H. Angewandte Chemie International Edition, Vol. 41, Issue 20 https://doi.org/10.1002/1521-3773(20021018)41:20<3839::AID-ANIE3839>3.0.CO;2-H	journal	October 2002
Alternierende Copolymerisation durch einen Grubbs-Initiator mit einem unsymmetrischen chiralen N-heterocyclischen Carbenliganden Vehlow, Kati; Wang, Dongren; Buchmeiser, Michael R. Angewandte Chemie, Vol. 120, Issue 14 https://doi.org/10.1002/ange.200704822	journal	March 2008
Synthesis of Discrete Oligomers by Sequential PET-RAFT Single-Unit Monomer Insertion Xu, Jiangtao; Fu, Changkui; Shanmugam, Sivaprakash Angewandte Chemie, Vol. 129, Issue 29 https://doi.org/10.1002/ange.201610223	journal	December 2016
Das Distortion/Interaction-Activation-Strain-Modell zur Analyse von Reaktionsgeschwindigkeiten Bickelhaupt, F. Matthias; Houk, Kendall N. Angewandte Chemie, Vol. 129, Issue 34 https://doi.org/10.1002/ange.201701486	journal	July 2017
Alternating Copolymerizations Using a Grubbs-Type Initiator with an Unsymmetrical, Chiral N-Heterocyclic Carbene Ligand Vehlow, Kati; Wang, Dongren; Buchmeiser, Michael R. Angewandte Chemie International Edition, Vol. 47, Issue 14 https://doi.org/10.1002/anie.200704822	journal	March 2008
Synthesis of Discrete Oligomers by Sequential PET-RAFT Single-Unit Monomer Insertion Xu, Jiangtao; Fu, Changkui; Shanmugam, Sivaprakash Angewandte Chemie International Edition, Vol. 56, Issue 29 https://doi.org/10.1002/anie.201610223	journal	December 2016
Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model Bickelhaupt, F. Matthias; Houk, Kendall N. Angewandte Chemie International Edition, Vol. 56, Issue 34 https://doi.org/10.1002/anie.201701486	journal	July 2017
Polycyclooctatetraene (polyacetylene) produced with a ruthenium olefin metathesis catalyst Scherman, Oren A.; Grubbs, Robert H. Synthetic Metals, Vol. 124, Issue 2-3 https://doi.org/10.1016/S0379-6779(01)00392-7	journal	October 2001
Precise Placement of Single Monomer Units in Living Ring-Opening Metathesis Polymerization Elling, Benjamin R.; Su, Jessica K.; Feist, John D. Chem, Vol. 5, Issue 10 https://doi.org/10.1016/j.chempr.2019.07.017	journal	October 2019
The ROMP toolbox upgraded Leitgeb, Anita; Wappel, Julia; Slugovc, Christian Polymer, Vol. 51, Issue 14, p. 2927-2946 https://doi.org/10.1016/j.polymer.2010.05.002	journal	June 2010
Precision Synthesis of Alternating Copolymers via Ring-Opening Polymerization of 1-Substituted Cyclobutenes Parker, Kathlyn A.; Sampson, Nicole S. Accounts of Chemical Research, Vol. 49, Issue 3 https://doi.org/10.1021/acs.accounts.5b00490	journal	February 2016
Ru-Catalyzed Isomerization Provides Access to Alternating Copolymers via Ring-Opening Metathesis Polymerization Tan, Li; Li, Guofang; Parker, Kathlyn A. Macromolecules, Vol. 48, Issue 14 https://doi.org/10.1021/acs.macromol.5b01058	journal	July 2015
Alternating Ring-Opening Metathesis Polymerization (AROMP) of Hydrophobic and Hydrophilic Monomers Provides Oligomers with Side-Chain Sequence Control Li, Guofang; Sampson, Nicole S. Macromolecules, Vol. 51, Issue 11 https://doi.org/10.1021/acs.macromol.8b00562	journal	May 2018
Synthesis of Cis , syndiotactic A -alt -B Copolymers from Two Enantiomerically Pure Trans -2,3-Disubstituted-5,6-Norbornenes Jang, Eun Sil; John, Jeremy M.; Schrock, Richard R. ACS Central Science, Vol. 2, Issue 9 https://doi.org/10.1021/acscentsci.6b00200	journal	August 2016
Iterative Radical Addition with a Special Monomer Carrying Bulky and Convertible Pendant: A New Concept toward Controlling the Sequence for Vinyl Polymers Oh, Dongyoung; Ouchi, Makoto; Nakanishi, Tomoya ACS Macro Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsmacrolett.6b00359	journal	May 2016
Efficient and Facile End Group Control of Living Ring-Opening Metathesis Polymers via Single Addition of Functional Cyclopropenes Elling, Benjamin R.; Xia, Yan ACS Macro Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acsmacrolett.8b00347	journal	May 2018
Synthesis of Stereoregular Polymers through Ring-Opening Metathesis Polymerization Schrock, Richard R. Accounts of Chemical Research, Vol. 47, Issue 8 https://doi.org/10.1021/ar500139s	journal	June 2014
Sequence-Controlled Polymers by Ruthenium-Mediated Ring-Opening Metathesis Polymerization Chang, Alice B.; Miyake, Garret M.; Grubbs, Robert H. ACS Symposium Series, Vol. 1170, p. 161-188 https://doi.org/10.1021/bk-2014-1170.ch011	book	September 2014
A survey of strained organic molecules Liebman, Joel F.; Greenberg, Arthur Chemical Reviews, Vol. 76, Issue 3 https://doi.org/10.1021/cr60301a002	journal	June 1976
Selectivity in Ring-Opening Metathesis Polymerization of Z -Cyclooctenes Catalyzed by a Second-generation Grubbs Catalyst Martinez, Henry; Miró, Pere; Charbonneau, Patrick ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300549u	journal	November 2012
Efficient and Recyclable Monomeric and Dendritic Ru-Based Metathesis Catalysts Garber, Steven B.; Kingsbury, Jason S.; Gray, Brian L. Journal of the American Chemical Society, Vol. 122, Issue 34 https://doi.org/10.1021/ja001179g	journal	August 2000
Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts: The Role of Ligands and Substrates from a Theoretical Perspective Adlhart, Christian; Chen, Peter Journal of the American Chemical Society, Vol. 126, Issue 11 https://doi.org/10.1021/ja0305757	journal	March 2004
The Elusive Mechanism of Olefin Metathesis Promoted by (NHC)Ru-Based Catalysts: A Trade between Steric, Electronic, and Solvent Effects Correa, Andrea; Cavallo, Luigi Journal of the American Chemical Society, Vol. 128, Issue 41 https://doi.org/10.1021/ja064924j	journal	October 2006
Scope of the Ring-Opening Metathesis Polymerization (ROMP) Reaction of 1-Substituted Cyclobutenes Song, Airong; Lee, Jae Chul; Parker, Kathlyn A. Journal of the American Chemical Society, Vol. 132, Issue 30 https://doi.org/10.1021/ja1037098	journal	August 2010
Synthesis of cis,syndiotactic ROMP Polymers Containing Alternating Enantiomers Flook, Margaret M.; Ng, Victor W. L.; Schrock, Richard R. Journal of the American Chemical Society, Vol. 133, Issue 6, p. 1784-1786 https://doi.org/10.1021/ja110949f	journal	January 2011
Regio- and Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted Cyclooctenes Kobayashi, Shingo; Pitet, Louis M.; Hillmyer, Marc A. Journal of the American Chemical Society, Vol. 133, Issue 15, p. 5794-5797 https://doi.org/10.1021/ja201644v	journal	March 2011
Isomeric Cyclopropenes Exhibit Unique Bioorthogonal Reactivities Kamber, David N.; Nazarova, Lidia A.; Liang, Yong Journal of the American Chemical Society, Vol. 135, Issue 37 https://doi.org/10.1021/ja407737d	journal	September 2013
Theory of 1,3-Dipolar Cycloadditions: Distortion/Interaction and Frontier Molecular Orbital Models Ess, Daniel H.; Houk, K. N. Journal of the American Chemical Society, Vol. 130, Issue 31 https://doi.org/10.1021/ja800009z	journal	August 2008
Synthesis of Copolymers by Alternating ROMP (AROMP) Song, Airong; Parker, Kathlyn A.; Sampson, Nicole S. Journal of the American Chemical Society, Vol. 131, Issue 10 https://doi.org/10.1021/ja809661k	journal	March 2009
Synthesis of Alternating trans -AB Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Alkylidenes Jeong, Hyangsoo; John, Jeremy M.; Schrock, Richard R. Journal of the American Chemical Society, Vol. 137, Issue 6 https://doi.org/10.1021/jacs.5b00221	journal	February 2015
Living Alternating Ring-Opening Metathesis Polymerization Based on Single Monomer Additions Elling, Benjamin R.; Xia, Yan Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b05497	journal	July 2015
Synthesis of cis,syndiotactic- A -alt -B Copolymers from Enantiomerically Pure Endo -2-Substituted-5,6-Norbornenes Jang, Eun Sil; John, Jeremy M.; Schrock, Richard R. Journal of the American Chemical Society, Vol. 139, Issue 14 https://doi.org/10.1021/jacs.7b01747	journal	March 2017
Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion Huang, Zixuan; Noble, Benjamin B.; Corrigan, Nathaniel Journal of the American Chemical Society, Vol. 140, Issue 41 https://doi.org/10.1021/jacs.8b08386	journal	September 2018
Benzoladderene Mechanophores: Synthesis, Polymerization, and Mechanochemical Transformation Yang, Jinghui; Horst, Matias; Romaniuk, Joseph A. H. Journal of the American Chemical Society, Vol. 141, Issue 16 https://doi.org/10.1021/jacs.9b01736	journal	April 2019
Living Polymerization Caught in the Act: Direct Observation of an Arrested Intermediate in Metathesis Polymerization Song, Jung-Ah; Park, Bohyun; Kim, Soohyung Journal of the American Chemical Society, Vol. 141, Issue 25 https://doi.org/10.1021/jacs.9b04019	journal	June 2019
Modeling Ring-Chain Equilibria in Ring-Opening Polymerization of Cycloolefins Chen, Zhong-Ren; Claverie, Jerome P.; Grubbs, Robert H. Macromolecules, Vol. 28, Issue 7 https://doi.org/10.1021/ma00111a007	journal	March 1995
Kinetics and thermodynamics of the metathesis reaction of cycloolefins. 2. Molecular weight distribution Reif, Lothar; Hoecker, Hartwig Macromolecules, Vol. 17, Issue 4 https://doi.org/10.1021/ma00134a070	journal	July 1984
Alternating Copolymerizations of Polar and Nonpolar Cyclic Olefins by Ring-Opening Metathesis Polymerization Ilker, M. Firat; Coughlin, E. Bryan Macromolecules, Vol. 35, Issue 1 https://doi.org/10.1021/ma011394x	journal	January 2002
Living Ring-Opening Metathesis Polymerization of Cyclopropenes Singh, Rojendra; Czekelius, Constantin; Schrock, Richard R. Macromolecules, Vol. 39, Issue 4 https://doi.org/10.1021/ma052560u	journal	February 2006
Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by Monoaryloxidepyrrolide (MAP) Catalysts Flook, Margaret M.; Gerber, Laura C. H.; Debelouchina, Galia T. Macromolecules, Vol. 43, Issue 18, p. 7515-7522 https://doi.org/10.1021/ma101375v	journal	September 2010
A Bicyclo[4.2.0]octene-Derived Monomer Provides Completely Linear Alternating Copolymers via Alternating Ring-Opening Metathesis Polymerization (AROMP) Tan, Li; Parker, Kathlyn A.; Sampson, Nicole S. Macromolecules, Vol. 47, Issue 19 https://doi.org/10.1021/ma5012039	journal	September 2014
Stereospecific Ring-Opening Metathesis Polymerization of 3-Methyl-3-phenylcylopropene by Molybdenum Alkylidene Initiators Singh, Rojendra; Schrock, Richard R. Macromolecules, Vol. 41, Issue 9 https://doi.org/10.1021/ma800280q	journal	May 2008
Homologous Poly(isobutylene)s: Poly(isobutylene)/High-Density Poly(ethylene) Hybrid Polymers Binder, Wolfgang H.; Kurzhals, Steffen; Pulamagatta, Bhanuprathap Macromolecules, Vol. 41, Issue 22 https://doi.org/10.1021/ma801465r	journal	November 2008
The Living ROMP of trans -Cyclooctene Walker, Ron; Conrad, Rosemary M.; Grubbs, Robert H. Macromolecules, Vol. 42, Issue 3 https://doi.org/10.1021/ma801693q	journal	February 2009
PC-Polyolefins: Synthesis and Assembly Behavior in Water Kratz, Katrina; Breitenkamp, Kurt; Hule, Rohan Macromolecules, Vol. 42, Issue 9 https://doi.org/10.1021/ma900653h	journal	May 2009
Utility of a Ruthenium Metathesis Catalyst for the Preparation of End-Functionalized Polybutadiene Hillmyer, Marc A.; Nguyen, SonBinh T.; Grubbs, Robert H. Macromolecules, Vol. 30, Issue 4 https://doi.org/10.1021/ma961316n	journal	February 1997
Ruthenium Alkylidene Initiated Living Ring-Opening Metathesis Polymerization (ROMP) of 3-Substituted Cyclobutenes Maughon, Bob R.; Grubbs, Robert H. Macromolecules, Vol. 30, Issue 12 https://doi.org/10.1021/ma961780s	journal	June 1997
Tuning the Steric Properties of a Metathesis Catalyst for Copolymerization of Norbornene and Cyclooctene toward Complete Alternation Torker, Sebastian; Müller, Andre; Sigrist, Raphael Organometallics, Vol. 29, Issue 12 https://doi.org/10.1021/om100185g	journal	June 2010
DFT Study of the Isomerization and Spectroscopic/Structural Properties of Ruthenacyclobutane Intermediates Relevant to Olefin Metathesis Rowley, Christopher N.; van der Eide, Edwin F.; Piers, Warren E. Organometallics, Vol. 27, Issue 23 https://doi.org/10.1021/om8008519	journal	December 2008
Conformational Analysis of Olefin−Carbene Ruthenium Metathesis Catalysts Benitez, Diego; Tkatchouk, Ekaterina; Goddard, William A. Organometallics, Vol. 28, Issue 8 https://doi.org/10.1021/om900041j	journal	April 2009
Alternating ring-opening metathesis polymerization by Grubbs-type catalysts with N -pentiptycenyl, N -alkyl-NHC ligands Vasiuta, Roman; Stockert, Alexander; Plenio, Herbert Chemical Communications, Vol. 54, Issue 14 https://doi.org/10.1039/C7CC08476E	journal	January 2018
Relevance of cis- and trans-dichloride Ru intermediates in Grubbs-II olefin metathesis catalysis (H2IMesCl2RuCHR) Benitez, Diego; Tkatchouk, Ekaterina; Goddard III, William A. Chemical Communications, Issue 46 https://doi.org/10.1039/b815665d	journal	January 2008
Ring-opening metathesis polymerization of 8-membered cyclic olefins Martinez, Henry; Ren, Ning; Matta, Megan E. Polymer Chemistry, Vol. 5, Issue 11 https://doi.org/10.1039/c3py01787g	journal	January 2014
Mechanochemical unzipping of insulating polyladderene to semiconducting polyacetylene Chen, Zhixing; Mercer, Jaron A. M.; Zhu, Xiaolei Science, Vol. 357, Issue 6350 https://doi.org/10.1126/science.aan2797	journal	August 2017
3-Hydroxymethyl-3-phenylcyclopropene Selvaraj, Ramajeyam Organic Syntheses, Vol. 91 https://doi.org/10.15227/orgsyn.091.0322	journal	January 2014

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