Metathesis catalysts and methods thereof

Schrock, Richard Royce; Yuan, Jian

Title: Metathesis catalysts and methods thereof

Patent · Tue Apr 19 00:00:00 EDT 2016

OSTI ID:1248013

Schrock, Richard Royce; Yuan, Jian

The present application provides, among other things, novel compounds for metathesis reactions, and methods for preparing and using provided compounds. In some embodiments, the present invention provides compounds having the structure of formula I or II. In some embodiments, the present invention provides methods for preparing a compound of formula I or II. In some embodiments, the present invention provides methods for using a provided compound. In some embodiments, a provided compound is useful for stereoselective ring-opening metathesis polymerization. In some embodiments, a provided metathesis method provides cis and/or isotactic polymers.

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

Sponsoring Organization:: USDOE

DOE Contract Number:: FG02-86ER13564

Assignee:: Massachusetts Institute of Technology (Cambridge, MA)

Patent Number(s):: 9,315,604

Application Number:: 14/248,712

OSTI ID:: 1248013

Resource Relation:: Patent File Date: 2014 Apr 09

Country of Publication:: United States

Language:: English

References (64)

Synthesis and ROMP Chemistry of Decafluoroterphenoxide Molybdenum Imido Alkylidene and Ethylene Complexes Yuan, Jian; Schrock, Richard R.; Gerber, Laura C. H. Organometallics, Vol. 32, Issue 10, p. 2983-2992 https://doi.org/10.1021/om400199u	journal	May 2013
Pentafluorophenylimido Alkylidene Complexes of Molybdenum and Tungsten Yuan, Jian; Schrock, Richard R.; Müller, Peter Organometallics, Vol. 31, Issue 13 https://doi.org/10.1021/om300408n	journal	June 2012
Room-Temperature Z -Selective Homocoupling of α-Olefins by Tungsten Catalysts Marinescu, Smaranda C.; Schrock, Richard R.; Müller, Peter Organometallics, Vol. 30, Issue 7 https://doi.org/10.1021/om200150c	journal	April 2011
Preparation of Tungsten-Based Olefin Metathesis Catalysts Supported on Alumina Yuan, Jian; Townsend, Erik M.; Schrock, Richard R. Advanced Synthesis & Catalysis, Vol. 353, Issue 11-12, p. 1985-1992 https://doi.org/10.1002/adsc.201100200	journal	July 2011
Monoaryloxide Pyrrolide (MAP) Imido Alkylidene Complexes of Molybdenum and Tungsten That Contain 2,6-Bis(2,5-R ₂ -pyrrolyl)phenoxide (R = i-Pr, Ph) Ligands and an Unsubstituted Metallacyclobutane on Its Way to Losing Ethylene Reithofer, Michael R.; Dobereiner, Graham E.; Schrock, Richard R. Organometallics, Vol. 32, Issue 9 https://doi.org/10.1021/om400114h	journal	April 2013
Synthesis, structure, and spectroscopic properties of copper( II ) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper( II ) perchlorate Addison, Anthony W.; Rao, T. Nageswara; Reedijk, Jan J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9840001349	journal	January 1984
Evaluation of Molybdenum and Tungsten Metathesis Catalysts for Homogeneous Tandem Alkane Metathesis Bailey, Brad C.; Schrock, Richard R.; Kundu, Sabuj Organometallics, Vol. 28, Issue 1 https://doi.org/10.1021/om800877q	journal	January 2009
Chemical transformations of cis -W(CO) ₄ (C ₅ H ₅ N) ₂ in the ring-opening metathesis polymerization of norbornene Bencze, L.; Bíró, N.; Szabó-Ravasz, B. Canadian Journal of Chemistry, Vol. 82, Issue 4 https://doi.org/10.1139/v04-007	journal	April 2004
Vinylcarbene Complexes of Titanocene Binger, Paul; Müller, Patrik; Benn, Reinhard Angewandte Chemie International Edition in English, Vol. 28, Issue 5, p. 610-611 https://doi.org/10.1002/anie.198906101	journal	May 1989
X-ray crystallographic studies on octahedral oxo alkylidene complexes of tungsten(VI): W(O)(CHCMe3)(PMe3)2Cl2 and W(O)(CHCMe3)(PEt3)2Cl2 Churchill, Melvyn Rowen; Rheingold, Arnold L.; Youngs, Wiley J. Journal of Organometallic Chemistry, Vol. 204, Issue 2 https://doi.org/10.1016/S0022-328X(00)84595-7	journal	January 1981
(2-Methoxy-1,3-phenylene)diboronic acid Dąbrowski, Marek; Luliński, Sergiusz; Serwatowski, Janusz Acta Crystallographica Section E Structure Reports Online, Vol. 64, Issue 2 https://doi.org/10.1107/S160053680800010X	journal	January 2008
Synthesis and Reactions of Tungsten Oxo Vinylalkylidene Complexes: Reactions of WCl ₂ (O)(PX ₃ ) (X = OMe, R) Precursors with 3,3-Diphenylcyclopropene ^† de la Mata, F. Javier; Grubbs, Robert H. Organometallics, Vol. 15, Issue 2 https://doi.org/10.1021/om950389c	journal	January 1996
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
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
Five-Coordinate Rearrangements of Metallacyclobutane Intermediates during Ring-Opening Metathesis Polymerization of 2,3-Dicarboalkoxynorbornenes by Molybdenum and Tungsten Monoalkoxide Pyrrolide Initiators Flook, Margaret M.; Börner, Janna; Kilyanek, Stefan M. Organometallics, Vol. 31, Issue 17, p. 6231-6243 https://doi.org/10.1021/om300530p	journal	August 2012
Simple, high yield syntheses of molybdenum(VI) bis(imido) complexes of the type Mo(NR)2Cl2(1,2-dimethoxyethane) Fox, Harold H.; Yap, Kimo B.; Robbins, Jennifer Inorganic Chemistry, Vol. 31, Issue 11 https://doi.org/10.1021/ic00037a056	journal	May 1992
Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis Goldman, Alan S.; Roy, Amy H.; Huang, Zheng Science, Vol. 312, Issue 5771, p. 257-261 https://doi.org/10.1126/science.1123787	journal	April 2006
Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture) Grubbs, Robert H. Angewandte Chemie International Edition, Vol. 45, Issue 23, p. 3760-3765 https://doi.org/10.1002/anie.200600680	journal	June 2006
Thermodynamics, Kinetics, and Mechanism of (silox) ₃ M(olefin) to (silox) ₃ M(alkylidene) Rearrangements (silox = ^t Bu ₃ SiO; M = Nb, Ta) Hirsekorn, Kurt F.; Veige, Adam S.; Marshak, Michael P. Journal of the American Chemical Society, Vol. 127, Issue 13 https://doi.org/10.1021/ja046180k	journal	April 2005
Dipyrrolyl Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts Hock, A. S.; Schrock, Richard R.; Hoveyda, Amir H. Journal of the American Chemical Society, Vol. 128, Issue 50 https://doi.org/10.1021/ja0665904	journal	December 2006
Highly Z - and Enantioselective Ring-Opening/Cross-Metathesis Reactions Catalyzed by Stereogenic-at-Mo Adamantylimido Complexes Ibrahem, Ismail; Yu, Miao; Schrock, Richard R. Journal of the American Chemical Society, Vol. 131, Issue 11 https://doi.org/10.1021/ja900097n	journal	March 2009
The ¹³C NMR spectra of poly(1‐pentenylene) and poly(1,3‐cyclopentylenevinylene) Ivin, Kenneth J.; Laverty, D. Theodore; Rooney, John J. Die Makromolekulare Chemie, Vol. 178, Issue 5, p. 1545-1560 https://doi.org/10.1002/macp.1977.021780527	journal	May 1977
Synthesis and characterization of tungsten oxo alkylidene complexes via the reaction of WCl2(O)[PX3]3 (PX3  P(OMe)3, PMe2Ph, PMePh2) with 4,8-dioxaspiro[2,5]oct-1-ene (ketalcyclopropene) Javier de la Mata, F. Journal of Organometallic Chemistry, Vol. 525, Issue 1-2 https://doi.org/10.1016/S0022-328X(96)06493-5	journal	November 1996
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
Highly Z -Selective Metathesis Homocoupling of Terminal Olefins Jiang, Annie J.; Zhao, Yu; Schrock, Richard R. Journal of the American Chemical Society, Vol. 131, Issue 46 https://doi.org/10.1021/ja908098t	journal	November 2009
Cationic Molybdenum Imido Alkylidene Complexes Jiang, Annie J.; Schrock, Richard R.; Müller, Peter Organometallics, Vol. 27, Issue 17 https://doi.org/10.1021/om800209b	journal	September 2008
Synthesis of tungsten vinyl alkylidene complexes via the reactions of WCl₂(NAr)(PX₃)₃ (X = R, OMe) precursors with 3,3-disubstituted cyclopropenes Johnson, Lynda K.; Grubbs, Robert H.; Ziller, Joseph W. Journal of the American Chemical Society, Vol. 115, Issue 18, p. 8130-8145 https://doi.org/10.1021/ja00071a026	journal	September 1993
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
Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum Marinescu, Smaranda C.; Ng, Victor W. L.; Lichtscheidl, Alejandro G. Organometallics, Vol. 31, Issue 17 https://doi.org/10.1021/om300585s	journal	August 2012
Syntheses and Structures of Molybdenum Imido Alkylidene Pyrrolide and Indolide Complexes Marinescu, Smaranda C.; Singh, Rojendra; Hock, Adam S. Organometallics, Vol. 27, Issue 24 https://doi.org/10.1021/om800816q	journal	December 2008
Simple Molybdenum(IV) Olefin Complexes of the Type Mo(NR)(X)(Y)(olefin) Marinescu, Smaranda C.; King, Annie J.; Schrock, Richard R. Organometallics, Vol. 29, Issue 24 https://doi.org/10.1021/om101003v	journal	December 2010
Catalytic Z-selective olefin cross-metathesis for natural product synthesis Meek, Simon J.; O’Brien, Robert V.; Llaveria, Josep Nature, Vol. 471, Issue 7339 https://doi.org/10.1038/nature09957	journal	March 2011
Practical suggestions for better crystal structures Müller, Peter Crystallography Reviews, Vol. 15, Issue 1 https://doi.org/10.1080/08893110802547240	journal	January 2009
Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media Nguyen, SonBinh T.; Johnson, Lynda K.; Grubbs, Robert H. Journal of the American Chemical Society, Vol. 114, Issue 10, p. 3974-3975 https://doi.org/10.1021/ja00036a053	journal	May 1992
Preparation of Well-Defined, Metathetically Active Oxo Alkylidene Complexes of Tungsten O'Donoghue, M. B.; Schrock, R. R.; LaPointe, A. M. Organometallics, Vol. 15, Issue 5 https://doi.org/10.1021/om950857i	journal	January 1996
Synthesis of Tungsten Oxo Alkylidene Complexes Peryshkov, Dmitry V.; Schrock, Richard R. Organometallics, Vol. 31, Issue 20, p. 7278-7286 https://doi.org/10.1021/om3008579	journal	October 2012
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
Olefin metathesis - a mechanistic study of high-valent Group VI catalysts Rappe, Anthony K.; Goddard, William A. Journal of the American Chemical Society, Vol. 104, Issue 2 https://doi.org/10.1021/ja00366a013	journal	January 1982
Catalytic Homologation of Vinyltributylstannane to Allyltributylstannane by Mo(IV) Complexes in the Presence of Ethylene Schrock, Richard R.; Duval-Lungulescu, M.; Tsang, W. C. Peter Journal of the American Chemical Society, Vol. 126, Issue 7 https://doi.org/10.1021/ja039173p	journal	February 2004
Olefin Metathesis Reactions Initiated by d ² Molybdenum or Tungsten Complexes Schrock, Richard R.; Lopez, Lourdes Pia H.; Hafer, Jillian Organometallics, Vol. 24, Issue 22 https://doi.org/10.1021/om050583r	journal	October 2005
Recent advances in olefin metathesis by molybdenum and tungsten imido alkylidene complexes Schrock, R. Journal of Molecular Catalysis A: Chemical, Vol. 213, Issue 1, p. 21-30 https://doi.org/10.1016/j.molcata.2003.10.060	journal	April 2004
Multiple Metal–Carbon Bonds for Catalytic Metathesis Reactions (Nobel Lecture) Schrock, Richard R. Angewandte Chemie International Edition, Vol. 45, Issue 23, p. 3748-3759 https://doi.org/10.1002/anie.200600085	journal	June 2006
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
Phase annealing in SHELX-90: direct methods for larger structures Sheldrick, G. M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 46, Issue 6, p. 467-473 https://doi.org/10.1107/S0108767390000277	journal	June 1990
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
Preparation and olefin-metathesis activity of cyclopentylidene-oxo initiator sites on a molybdenum carbide surface Siaj, Mohamed; Temprano, Israel; Dubuc, Nathalie Journal of Organometallic Chemistry, Vol. 691, Issue 24-25, p. 5497-5504 https://doi.org/10.1016/j.jorganchem.2006.09.033	journal	December 2006
Z -Selective Metathesis Homocoupling of 1,3-Dienes by Molybdenum and Tungsten Monoaryloxide Pyrrolide (MAP) Complexes Townsend, Erik M.; Schrock, Richard R.; Hoveyda, Amir H. Journal of the American Chemical Society, Vol. 134, Issue 28 https://doi.org/10.1021/ja303220j	journal	July 2012
Investigations of Reactions between Chiral Molybdenum Imido Alkylidene Complexes and Ethylene: Observation of Unsolvated Base-Free Methylene Complexes, Metalacyclobutane and Metalacyclopentane Complexes, and Molybdenum(IV) Olefin Complexes Tsang, W. C. Peter; Jamieson, Jennifer Y.; Aeilts, Sarah L. Organometallics, Vol. 23, Issue 9 https://doi.org/10.1021/om030636+	journal	March 2004
Efficient and Selective Formation of Macrocyclic Disubstituted Z Alkenes by Ring-Closing Metathesis (RCM) Reactions Catalyzed by Mo- or W-Based Monoaryloxide Pyrrolide (MAP) Complexes: Applications to Total Syntheses of Epilachnene, Yuzu Lactone, Ambretto Wang, Chenbo; Yu, Miao; Kyle, Andrew F. Chemistry - A European Journal, Vol. 19, Issue 8 https://doi.org/10.1002/chem.201204045	journal	January 2013
Molybdenum-Based Complexes with Two Aryloxides and a Pentafluoroimido Ligand: Catalysts for Efficient Z-Selective Synthesis of a Macrocyclic Trisubstituted Alkene by Ring-Closing Metathesis Wang, Chenbo; Haeffner, Fredrik; Schrock, Richard R. Angewandte Chemie International Edition, Vol. 52, Issue 7, p. 1939-1943 https://doi.org/10.1002/anie.201209180	journal	January 2013
Enol Ethers as Substrates for Efficient Z - and Enantioselective Ring-Opening/Cross-Metathesis Reactions Promoted by Stereogenic-at-Mo Complexes: Utility in Chemical Synthesis and Mechanistic Attributes Yu, Miao; Ibrahem, Ismail; Hasegawa, Masayuki Journal of the American Chemical Society, Vol. 134, Issue 5 https://doi.org/10.1021/ja210946z	journal	January 2012
Asymmetric ring-closing metathesis reactions Schrock, Richard R.; Alexander, John https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/6121473 US Patent Document 6,121,473	patent	September 2000
Olefin metathesis catalysts and related methods Hock, Adam S.; Schrock, Richard R. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/7932397 US Patent Document 7,932,397	patent	April 2011
Catalysts and processes for the formation of terminal olefins by ethenolysis Schrock, Richard R.; Marinescu, Smaranda C.; Hoveyda, Amir H. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/8222469 US Patent Document 8,222,469	patent	July 2012
Olefin metathesis catalysts and related methods Hock, Adam S.; Schrock, Richard R. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/8350073 US Patent Document 8,350,073	patent	January 2013
Highly Z-selective olefins metathesis Schrock, Richard R.; King, Annie J.; Zhao, Yu https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/8362311 US Patent Document 8,362,311	patent	January 2013
Complexes for use in metathesis reactions Hoveyda, Amir H.; Schrock, Richard R.; Meek, Simon J. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/8546500 US Patent Document 8,546,500	patent	October 2013
Efficient methods for Z- or cis-selective cross-metathesis Hoveyda, Amir H.; Meek, Simon J.; O'Brien, Robert V. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/8598400 US Patent Document 8,598,400	patent	December 2013
Olefin metathesis catalysts and related methods Hock, Adam S.; Schrock, Richard R. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/8829219 US Patent Document 8,829,219	patent	September 2014
Z-selective ring-closing metathesis reactions Hoveyda, Amir H.; Yu, Miao; Wang, Chenbo https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/9073801 US Patent Document 9,073,801	patent	July 2015
Highly Z-selective olefins metathesis Schrock, Richard R.; King, Annie J.; Zhao, Yu https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/9079173 US Patent Document 9,079,173	patent	July 2015
Tungsten oxo alkylidene complexes for Z selective olefin metathesis Schrock, Richard R.; Peryshkov, Dmitry Vyacheslavovich; Hoveyda, Amir H. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/9085595 US Patent Document 9,085,595	patent	July 2015
Tungsten OXO Alkylidene Complexes for Z Selective Olefin Metathesis Schrock, Richard Royce; Peryshkov, Dmitry Vyacheslavovich; Hoveyda, Amir H. https://doi.org/https://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/20130116434 US Patent Application 13/671109; 20130116434	patent-application	May 2013

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