- Reductive Elimination to Form C(sp3)-N Bonds from Palladium(II) Primary Alkyl Complexes
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Reductive eliminations to form alkyl-nitrogen bonds are rare, and examples of this reaction from isolated complexes containing simple, unstabilized primary alkyl groups have not been observed. We report the synthesis of stable neopentylpalladium(II) anilido and methyleneamido complexes that undergo reductive elimination to form the C(sp3)-N bonds in N-neopentyl anilines and N-neopentyl imines, respectively. The synthesis and isolation of these complexes were enabled by weak chelation of palladium by P,O ancillary ligands. DFT calculations suggest that neopentylpalladium(II) complexes undergo reductive elimination by a concerted mechanism resembling a migration of the alkyl ligand to the nitrogen either following initial dissociation of the oxygen donor or in concert with lengthening of the Pd-O bond, depending on the identities of the reacting and ancillary ligands.
- Peacock, D. Matthew,Jiang, Quan,Cundari, Thomas R.,Hartwig, John F.
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supporting information
p. 3243 - 3247
(2018/10/05)
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- Study on the electronic effect on coordinating donors in heptacoordinate trichlorogermanes
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Trichloro[tris(2,5-dimethoxyphenyl)methyl]germane (1a), trichloro[tris(3-fluoro-6-methoxyphenyl)methyl]germane (1b), and trichloro[tris(2-methoxy-5-trifluoromethylphenyl)methyl]germane (1c) were synthesized. X-ray crystallographic analyses of 1a-c revealed their heptacoordinate geometries around the germanium atoms. The interatomic distances between the oxygen atoms and the central germanium atoms in the crystalline state were not significantly affected by change of functional groups on the benzene rings, while the optimized structures by theoretical calculations and Atoms in Molecules (AIM) analysis indicated linear relationship between the donating ability of functional groups and the O?Ge interatomic interactions.
- Iwanaga, Kohei,Kobayashi, Junji,Kawashima, Takayuki
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p. 10127 - 10132
(2008/02/13)
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- Structure-activity relationship studies of novel benzophenones leading to the discovery of a potent, next generation HIV nonnucleoside reverse transcriptase inhibitor
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Despite the progress of the past two decades, there is still considerable need for safe, efficacious drugs that target human immunodeficiency virus (HIV). This is particularly true for the growing number of patients infected with virus resistant to currently approved HIV drugs. Our high throughput screening effort identified a benzophenone template as a potential nonnucleoside reverse transcriptase inhibitor (NNRTI). This manuscript describes our extensive exploration of the benzophenone structure-activity relationships, which culminated in the identification of several compounds with very potent inhibition of both wild type and clinically relevant NNRTI-resistant mutant strains of HIV. These potent inhibitors include 70h (GW678248), which has in vitro antiviral assay IC50 values of 0.5 nM against wild-type HIV, 1 nM against the K103N mutant associated with clinical resistance to efavirenz, and 0.7 nM against the Y181C mutant associated with clinical resistance to nevirapine. Compound 70h has also demonstrated relatively low clearance in intravenous pharmacokinetic studies in three species, and it is the active component of a drug candidate which has progressed to phase 2 clinical studies.
- Romines, Karen R.,Freeman, George A.,Schaller, Lee T.,Cowan, Jill R.,Gonzales, Steve S.,Tidwell, Jeffrey H.,Andrews III, Clarence W.,Stammers, David K.,Hazen, Richard J.,Ferris, Robert G.,Short, Steven A.,Chan, Joseph H.,Boone, Lawrence R.
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p. 727 - 739
(2007/10/03)
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