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Title: Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations

Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(Ox Me2) 2C 5H 5 (Bo MCpH; Ox Me2 = 4,4-dimethyl-2-oxazoline) and MeC(Ox Me2) 2C 5Me 4H (Bo MCp tetH) are synthesized from C 5R 4HI (R = H, Me) and MeC(Ox Me2) 2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. Bo MCpH and Bo MCp tetH react with MgMe 2(O 2C 4H 8) 2 to give the magnesium methyl complexes {Bo MCp}MgMe and {Bo MCp tet}MgMe. Bo MCpH and Bo MCp tetH are converted to Bo MCpTl and Bo MCp tetTl by reaction with TlOEt. The thallium derivatives react with TiCl 3(THF) 3 to provide [{Bo MCp}TiCl(μ-Cl)] 2 and [{Bo MCptet}TiCl(μ-Cl)] 2, the former of which is crystallographically characterized as a dimeric species. Bo MCpH and Zr(NMe 2) 4 react to eliminate dimethylamine and afford {Bo MCp}Zr(NMe 2) 3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {Bo MCp}Zr(NMe 2) 3, {Bo MCp}MgMe, and {Bo MCp tet}MgMe are efficient catalysts formore » the hydroamination/cyclization of aminoalkenes under mild conditions.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Publication Date:
Report Number(s):
IS-J-8905
Journal ID: ISSN 0276-7333
Grant/Contract Number:
AC02-07CH11358
Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 34; Journal Issue: 23; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1240912

Eedugurala, Naresh, Hovey, Megan, Ho, Hung -An, Jana, Barun, Lampland, Nicole L., Ellern, Arkady, and Sadow, Aaron D.. Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations. United States: N. p., Web. doi:10.1021/acs.organomet.5b00771.
Eedugurala, Naresh, Hovey, Megan, Ho, Hung -An, Jana, Barun, Lampland, Nicole L., Ellern, Arkady, & Sadow, Aaron D.. Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations. United States. doi:10.1021/acs.organomet.5b00771.
Eedugurala, Naresh, Hovey, Megan, Ho, Hung -An, Jana, Barun, Lampland, Nicole L., Ellern, Arkady, and Sadow, Aaron D.. 2015. "Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations". United States. doi:10.1021/acs.organomet.5b00771. https://www.osti.gov/servlets/purl/1240912.
@article{osti_1240912,
title = {Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations},
author = {Eedugurala, Naresh and Hovey, Megan and Ho, Hung -An and Jana, Barun and Lampland, Nicole L. and Ellern, Arkady and Sadow, Aaron D.},
abstractNote = {Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(OxMe2)2C5H5 (BoMCpH; OxMe2 = 4,4-dimethyl-2-oxazoline) and MeC(OxMe2)2C5Me4H (BoMCptetH) are synthesized from C5R4HI (R = H, Me) and MeC(OxMe2)2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. BoMCpH and BoMCptetH react with MgMe2(O2C4H8)2 to give the magnesium methyl complexes {BoMCp}MgMe and {BoMCptet}MgMe. BoMCpH and BoMCptetH are converted to BoMCpTl and BoMCptetTl by reaction with TlOEt. The thallium derivatives react with TiCl3(THF)3 to provide [{BoMCp}TiCl(μ-Cl)]2 and [{BoMCptet}TiCl(μ-Cl)]2, the former of which is crystallographically characterized as a dimeric species. BoMCpH and Zr(NMe2)4 react to eliminate dimethylamine and afford {BoMCp}Zr(NMe2)3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {BoMCp}Zr(NMe2)3, {BoMCp}MgMe, and {BoMCptet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.},
doi = {10.1021/acs.organomet.5b00771},
journal = {Organometallics},
number = 23,
volume = 34,
place = {United States},
year = {2015},
month = {11}
}