Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations
Abstract
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.
- Authors:
-
- Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)
- OSTI Identifier:
- 1240912
- Report Number(s):
- IS-J-8905
Journal ID: ISSN 0276-7333
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organometallics
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 23; Journal ID: ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
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., 2015.
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. https://doi.org/10.1021/acs.organomet.5b00771
Eedugurala, Naresh, Hovey, Megan, Ho, Hung -An, Jana, Barun, Lampland, Nicole L., Ellern, Arkady, and Sadow, Aaron D. Wed .
"Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations". United States. https://doi.org/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 = {Wed Nov 25 00:00:00 EST 2015},
month = {Wed Nov 25 00:00:00 EST 2015}
}
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