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Dramatic improvement in catalyst loadings and molar ratios of coupling partners for Ni/Cr-mediated coupling reactions: heterobimetallic catalysts.

ABSTRACT: Two new ligands 1a,b are reported. Upon treatment with 1 equiv of NiCl(2) x (MeOCH(2))(2), 1a,b give the corresponding Ni complexes. X-ray analysis of 1a x NiCl(2) established that the NiCl(2) is selectively coordinated to the phenanthroline nitrogens. Ni/Cr heterobimetallic catalysts 1a,b x CrCl(2)/NiCl(2), prepared from 1a,b x NiCl(2), have been shown to behave exceptionally well in catalytic asymmetric Ni/Cr-mediated couplings, with highlights including the following: (1) 1-2 mol % catalyst is sufficient to complete the coupling; (2) only negligible amounts of the dimers, byproducts formed through the alkenyl Ni species, are observed; (3) the coupling goes to completion even with a 1:1 molar ratio of the coupling partners; and (4) the asymmetric induction is practically identical with that obtained from the coupling with the Cr catalysts prepared from (S)-sulfonamides 2a,b. The scope of the new Ni/Cr heterobimetallic catalysts was briefly studied using four additional aldehydes. The applicability of the new catalysts to polyfunctional substrates was demonstrated by two C-C bond formations chosen from the halichondrin/E7389 synthesis as examples.

SUBMITTER: Liu X

PROVIDER: S-EPMC2784119 | biostudies-literature | 2009 Nov

REPOSITORIES: biostudies-literature

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Dramatic improvement in catalyst loadings and molar ratios of coupling partners for Ni/Cr-mediated coupling reactions: heterobimetallic catalysts.

Liu Xiang X Henderson James A JA Sasaki Takeo T Kishi Yoshito Y

Journal of the American Chemical Society 20091101 46

Two new ligands 1a,b are reported. Upon treatment with 1 equiv of NiCl(2) x (MeOCH(2))(2), 1a,b give the corresponding Ni complexes. X-ray analysis of 1a x NiCl(2) established that the NiCl(2) is selectively coordinated to the phenanthroline nitrogens. Ni/Cr heterobimetallic catalysts 1a,b x CrCl(2)/NiCl(2), prepared from 1a,b x NiCl(2), have been shown to behave exceptionally well in catalytic asymmetric Ni/Cr-mediated couplings, with highlights including the following: (1) 1-2 mol % catalyst i ...[more]

PMID: 19874019

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Project description:Mammalian molar crowns form a module in which measurements of size for individual teeth within a tooth row covary with one another. Molar crown size covariation is proposed to fit the inhibitory cascade model (ICM) or its variant the molar module component (MMC) model, but the inability of the former model to fit across biological scales is a concern in the few cases where it has been tested in Primates. The ICM has thus far failed to explain patterns of intraspecific variation, an intermediate biological scale, even though it explains patterns at both smaller organ-level and larger between-species biological scales. Studies of this topic in a much broader range of taxa are needed, but the properties of a sample appropriate for testing the ICM at the intraspecific level are unclear. Here, we assess intraspecific variation in relative molar sizes of the cotton mouse, Peromyscus gossypinus, to further test the ICM and to develop recommendations for appropriate sampling protocols in future intraspecific studies of molar size variation across Mammalia. To develop these recommendations, we model the sensitivity of estimates of molar ratios to sample size and simulate the use of composite molar rows when complete ones are unavailable. Similar to past studies on primates, our results show that intraspecific variance structure of molar ratios within the rodent P. gossypinus does not meet predictions of the ICM or MMC. When we extend these analyses to include the MMC, one model does not fit observed patterns of variation better than the other. Standing variation in molar size ratios is relatively constant across mammalian samples containing all three molars. In future studies, analyzing average ratio values will require relatively small minimum sample sizes of two or more complete molar rows. Even composite-based estimates from four or more specimens per tooth position can accurately estimate mean molar ratios. Analyzing variance structure will require relatively large sample sizes of at least 40-50 complete specimens, and composite molar rows cannot accurately reconstruct variance structure of ratios in a sample. Based on these results, we propose guidelines for intraspecific studies of molar size covariation. In particular, we note that the suitability of composite specimens for averaging mean molar ratios is promising for the inclusion of isolated molars and incomplete molar rows from the fossil record in future studies of the evolution of molar modules, as long as variance structure is not a key component of such studies.

Dataset Information

Dramatic improvement in catalyst loadings and molar ratios of coupling partners for Ni/Cr-mediated coupling reactions: heterobimetallic catalysts.

Publications

Dramatic improvement in catalyst loadings and molar ratios of coupling partners for Ni/Cr-mediated coupling reactions: heterobimetallic catalysts.

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