title: Z-Selective ethenolysis with a ruthenium metathesis catalyst: experiment and theory.
abstract: The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.
authors.affiliation: Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Miyazaki
authors.forename: Myles B
authors.initials: MB
authors.lastname: Herbert
authors.forename: Peng
authors.initials: P
authors.lastname: Liu
authors.forename: Xiaofei
authors.initials: X
authors.lastname: Dong
authors.forename: Xiufang
authors.initials: X
authors.lastname: Xu
authors.forename: Benjamin K
authors.initials: BK
authors.lastname: Keitz
authors.forename: Thay
authors.initials: T
authors.lastname: Ung
authors.forename: Garik
authors.initials: G
authors.lastname: Mkrtumyan
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.forename: Robert H
authors.initials: RH
authors.lastname: Grubbs
mesh_terms: D002384:Catalysis; D005030:Ethylenes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D005030:Ethylenes; D009942:Organometallic Compounds; D012428:Ruthenium; C036216:ethylene
references.citation: J Am Chem Soc. 2005 Sep 7;127(35):12218-9
references.pmid: 16131188
references.citation: Org Lett. 2007 May 10;9(10):1967-70
references.pmid: 17428063
references.citation: J Am Chem Soc. 2006 Oct 18;128(41):13352-3
references.pmid: 17031936
references.citation: J Am Chem Soc. 2012 Feb 1;134(4):2040-3
references.pmid: 22239675
references.citation: Chem Commun (Camb). 2008 Dec 14;(46):6194-6
references.pmid: 19082117
references.citation: Chemistry. 2002 Sep 2;8(17):3962-75
references.pmid: 12360937
references.citation: J Am Chem Soc. 2006 May 31;128(21):6952-64
references.pmid: 16719476
references.citation: J Am Chem Soc. 2012 Jan 25;134(3):1464-7
references.pmid: 22229694
references.citation: J Am Chem Soc. 2011 Jun 8;133(22):8525-7
references.pmid: 21563826
references.citation: J Am Chem Soc. 2011 May 18;133(19):7490-6
references.pmid: 21510645
references.citation: J Am Chem Soc. 2012 Jan 11;134(1):693-9
references.pmid: 22097946
references.citation: J Am Chem Soc. 2012 May 9;134(18):7861-6
references.pmid: 22500642
references.citation: Beilstein J Org Chem. 2011 Jan 11;7:40-5
references.pmid: 21286393
references.citation: Angew Chem Int Ed Engl. 2002 Dec 2;41(23):4484-7
references.pmid: 12458513
references.citation: J Am Chem Soc. 2004 Mar 24;126(11):3496-510
references.pmid: 15025477
references.citation: J Am Chem Soc. 2011 Aug 3;133(30):11512-4
references.pmid: 21718001
references.citation: Angew Chem Int Ed Engl. 2013 Jan 2;52(1):310-4
references.pmid: 23055437
references.citation: Organometallics. 2008 Jan 12;27(4):563-566
references.pmid: 18584055
references.citation: J Am Chem Soc. 2011 Feb 16;133(6):1784-6
references.pmid: 21265524
references.citation: Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
references.pmid: 9944570
references.citation: J Am Chem Soc. 2013 Jan 9;135(1):94-7
references.pmid: 23244210
references.citation: J Am Chem Soc. 2002 Jul 31;124(30):8965-73
references.pmid: 12137552
references.citation: J Am Chem Soc. 2009 Aug 12;131(31):10840-1
references.pmid: 19618951
references.citation: J Am Chem Soc. 2011 Jun 29;133(25):9686-8
references.pmid: 21649443
references.citation: J Am Chem Soc. 2007 Jun 27;129(25):7961-8
references.pmid: 17547403
references.citation: Acc Chem Res. 2008 Feb;41(2):157-67
references.pmid: 18186612
references.citation: Nature. 2011 Nov 02;479(7371):88-93
references.pmid: 22051677
references.citation: Dalton Trans. 2011 Feb 7;40(5):1061-72
references.pmid: 21161092
references.citation: Dalton Trans. 2005 Sep 21;(18):2982-4
references.pmid: 16127490
references.citation: Nature. 2011 Mar 24;471(7339):461-6
references.pmid: 21430774
references.citation: J Am Chem Soc. 2009 Nov 25;131(46):16630-1
references.pmid: 19919135
references.citation: J Am Chem Soc. 2008 Apr 9;130(14):4808-14
references.pmid: 18341339
references.citation: Dalton Trans. 2005 Sep 7;(17):2849-58
references.pmid: 16094473
references.citation: Angew Chem Int Ed Engl. 2005 Sep 19;44(37):5974-8
references.pmid: 16094683
references.citation: Proc Natl Acad Sci U S A. 2012 Sep 4;109(36):14332-6
references.pmid: 22912408
references.citation: J Am Chem Soc. 2013 Jan 30;135(4):1276-9
references.pmid: 23317178
references.citation: J Am Chem Soc. 2009 Jun 17;131(23):7962-3
references.pmid: 19462947
references.citation: J Am Chem Soc. 2004 Aug 11;126(31):9592-600
references.pmid: 15291563
references.citation: J Phys Chem B. 2009 May 7;113(18):6378-96
references.pmid: 19366259