Stereoselective Ring-Opening Metathesis Polymerization (ROMP) of Methyl- N -(1-phenylethyl)-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate by Molybdenum and Tungsten Initiators

Jeong, Hyangsoo; Ng, Victor W.  L.; Börner, Janna; Schrock, Richard R.

doi:10.1021/acs.macromol.5b00264

Stereoselective Ring-Opening Metathesis Polymerization (ROMP) of Methyl- N -(1-phenylethyl)-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate by Molybdenum and Tungsten Initiators

Journal Article · Tue Mar 17 00:00:00 EDT 2015 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5b00264· OSTI ID:1557799

Jeong, Hyangsoo ^[1]; Ng, Victor W. L. ^[2]; Börner, Janna ^[2]; Schrock, Richard R. ^[2]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Office of Scientific and Technical Information (OSTI)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Ring-opening metathesis polymerization (ROMP) of methyl-N-(1-phenylethyl)-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate (PhEtNNBE; (S) and racemic) was researched employing six molybdenum and tungsten imido alkylidene initiators and two tungsten oxo alkylidene initiators. Of the six initiators that we introduced should yield cis,syndiotactic-poly[(S)-PhEtNNBE], two molybdenum OHMT alkylidene initiators, Mo(NR)(CHMe₂Ph)(pyr)(OHMT) (R = 1-adamantyl (Ad) or 2,6-Me₂C₆H₃ (Ar'); OHMT = O-2,6-mesityl₂C₆H₃; pyr = pyrrolide), and two tungsten oxo alkylidene initiators, W(O)(CHMe₂Ph)(2,5-dimethylpyrrolide)(PMe₂Ph)(OR) (OR = OHMT or (R)-OBr₂Bitet where (R)-Br₂BitetOH = (R)-3,3'-dibromo-2'-(tert-butyldimethylsilyloxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2-ol), produced essentially pure cis,syndiotactic-poly[(S)-PhEtNNBE]. Essentially pure cis,isotactic-poly[(S)-PhEtNNBE] was formed when (S)-PhEtNNBE was polymerized by Mo(NAr')(CHCMe₂Ph)(OBiphen_CF3)(thf) or W(NAr')(CHCMe₂Ph)((S)-OBiphen_Me) (OBiphen_CF3= 3,3'-di-tert-butyl-5,5'-bistrifluoromethyl-6,6'-dimethyl-1,1'-biphenyl-2,2'-diolate; (S)-OBiphen_Me = 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-1,1'-biphenyl-2,2'-diolate). The best initiator for ROMP of rac-PhEtNNBE was Mo(NAd)(CHMe₂Ph)(pyr)(OHMT) at 0 °C, which led to a polymer that is biased (~80%) toward a cis,syndiotactic structure and that contains alternating enantiomers in the chain (cis,syndio,alt-poly[(rac)-PhEtNNBE]).

View Accepted Manuscript (DOE)

Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-86ER13564

OSTI ID:: 1557799

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 7 Vol. 48; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (26)

Molybdenum and Tungsten Imido Alkylidene Complexes as Efficient Olefin-Metathesis Catalysts Schrock, Richard R.; Hoveyda, Amir H. Angewandte Chemie International Edition, Vol. 42, Issue 38, p. 4592-4633 https://doi.org/10.1002/anie.200300576	journal	October 2003
Stereomutation in Trigonal-Bipyramidal Systems: A Unified Picture Moberg, Christina Angewandte Chemie International Edition, Vol. 50, Issue 44 https://doi.org/10.1002/anie.201103375	journal	August 2011
Asymmetric aza-diels-alder reaction using the chiral 1-phenyl ethyl imine of methyl glyoxylate Stella, L.; Abraham, H.; Feneau-Dupont, J. Tetrahedron Letters, Vol. 31, Issue 18 https://doi.org/10.1016/0040-4039(90)80136-A	journal	January 1990
Ring opening metathesis polymerization of methyl-N-(1-phenylethyl)-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate Schitter, Regina M. E.; Steinhäusler, Thomas; Stelzer, Franz Journal of Molecular Catalysis A: Chemical, Vol. 115, Issue 1 https://doi.org/10.1016/S1381-1169(96)00081-7	journal	January 1997
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
High Oxidation State Multiple Metal−Carbon Bonds Schrock, Richard R. Chemical Reviews, Vol. 102, Issue 1 https://doi.org/10.1021/cr0103726	journal	January 2002
Recent Advances in High Oxidation State Mo and W Imido Alkylidene Chemistry Schrock, Richard R. Chemical Reviews, Vol. 109, Issue 8 https://doi.org/10.1021/cr800502p	journal	August 2009
Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts ^† Vougioukalakis, Georgios C.; Grubbs, Robert H. Chemical Reviews, Vol. 110, Issue 3 https://doi.org/10.1021/cr9002424	journal	March 2010
Alkylidene and Metalacyclic Complexes of Tungsten that Contain a Chiral Biphenoxide Ligand. Synthesis, Asymmetric Ring-Closing Metathesis, and Mechanistic Investigations Tsang, W. C. Peter; Hultzsch, Kai C.; Alexander, John B. Journal of the American Chemical Society, Vol. 125, Issue 9 https://doi.org/10.1021/ja0210603	journal	March 2003
Understanding d ⁰ -Olefin Metathesis Catalysts: Which Metal, Which Ligands? Poater, Albert; Solans-Monfort, Xavier; Clot, Eric Journal of the American Chemical Society, Vol. 129, Issue 26 https://doi.org/10.1021/ja070625y	journal	July 2007
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
Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes Peryshkov, Dmitry V.; Schrock, Richard R.; Takase, Michael K. Journal of the American Chemical Society, Vol. 133, Issue 51, p. 20754-20757 https://doi.org/10.1021/ja210349m	journal	December 2011
Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators Forrest, William P.; Weis, Jonathan G.; John, Jeremy M. Journal of the American Chemical Society, Vol. 136, Issue 31 https://doi.org/10.1021/ja506446n	journal	July 2014
Inversion of Configuration at the Metal in Diastereomeric Imido Alkylidene Monoaryloxide Monopyrrolide Complexes of Molybdenum Marinescu, Smaranda C.; Schrock, Richard R.; Li, Bo Journal of the American Chemical Society, Vol. 131, Issue 1 https://doi.org/10.1021/ja808308e	journal	January 2009
Fundamental Studies of Tungsten Alkylidene Imido Monoalkoxidepyrrolide Complexes Jiang, Annie J.; Simpson, Jeffrey H.; Müller, Peter Journal of the American Chemical Society, Vol. 131, Issue 22 https://doi.org/10.1021/ja9012694	journal	June 2009
Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex Flook, Margaret M.; Jiang, Annie J.; Schrock, Richard R. Journal of the American Chemical Society, Vol. 131, Issue 23, p. 7962-7963 https://doi.org/10.1021/ja902738u	journal	June 2009
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
Molybdenum Imido Alkylidene Metathesis Catalysts That Contain Electron-Withdrawing Biphenolates or Binaphtholates Singh, Rojendra; Czekelius, Constantin; Schrock, Richard R. Organometallics, Vol. 26, Issue 10 https://doi.org/10.1021/om061134+	journal	April 2007
Fundamental Studies of Molybdenum and Tungsten Methylidene and Metallacyclobutane Complexes ^† Schrock, Richard R.; Jiang, Annie J.; Marinescu, Smaranda C. Organometallics, Vol. 29, Issue 21 https://doi.org/10.1021/om100363g	journal	November 2010
Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes Lichtscheidl, Alejandro G.; Ng, Victor W. L.; Müller, Peter Organometallics, Vol. 31, Issue 12 https://doi.org/10.1021/om300353e	journal	May 2012
Syntheses of Tungsten tert-Butylimido and Adamantylimido Alkylidene Complexes Employing Pyridinium Chloride As the Acid Jeong, Hyangsoo; Axtell, Jonathan C.; Török, Bela Organometallics, Vol. 31, Issue 18, p. 6522-6525 https://doi.org/10.1021/om300799q	journal	August 2012
Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands Townsend, Erik M.; Hyvl, Jakub; Forrest, William P. Organometallics, Vol. 33, Issue 19 https://doi.org/10.1021/om500655n	journal	September 2014
Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S. Nature, Vol. 456, Issue 7224 https://doi.org/10.1038/nature07594	journal	November 2008
Transition metal–carbon multiple bonds Schrock, Richard R. Journal of the Chemical Society, Dalton Transactions, Issue 18 https://doi.org/10.1039/b104609h	journal	January 2001
Synthesis of stereoregular ROMP polymers using molybdenum and tungsten imido alkylidene initiators Schrock, Richard R. Dalton Transactions, Vol. 40, Issue 29, p. 7484-7495 https://doi.org/10.1039/c1dt10215j	journal	May 2011
Synthesis of a poly(2-azanorbornene) with a high degree of cis-TT-stereoregularity and a regular secondary solution structure Rossegger, Elisabeth; Oláh, László; Fischer, Roland Polymer Chemistry, Vol. 3, Issue 10 https://doi.org/10.1039/c2py20219k	journal	January 2012

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