
By Gold, Victor
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16). 2 CrX2 I Ni(0) + CrX3 (a) R CrX2 CrX3 Ni I OCrX2 RCHO CrX2 I CrX2 X Ni + NiX2 (b) I NiX2 + 2 CrX2 Ni(0) + 2 CrX3 (c) The NHK reaction catalyzed by an Ni(0) species: the second ‘Nickel Effect’. 16. vinylchromium(III) species that involves transmetallation between vinylnickel(II) and Cr(III)X3 ; c) Reduction process of Ni(II) to Ni(0) with 2 equiv. Cr(II). The NHK reaction shows a wide compatibility with functional groups, chemoselectivity (aldehydes g ketones), and a low basicity; hence the reaction has been widely used for the total synthesis of many natural products of structural complexity.
A) Y. Sato, T. Takanashi, M. Hoshiba, M. Mori, J. Organomet. Chem. 2003, 688, 36–48; (b) Y. Sato, N. Saito, M. Mori, J Org. Chem. 2002, 67, 656–662; (c) Y. Sato, M. Takimoto, M. Mori, Miwako. Yuki Gosei Kagaku Kyokaishi, 2001, 59, 576– 588; (d) M. Takimoto, Y. Hiraga, Y. Sato, M. Mori, Tetrahedron Lett. 1998, 39, 4543–4546; (e) Y. Sato, M. Takimoto, K. Hayashi, T. Katsuhara, K. Takagi, M. Mori, J. Am. Chem. Soc. 1994, 116, 9771–9772. ¨ rstner, N. Shi, J. Am. Chem. (a) A. Fu Soc. 1996, 118, 2533–2534; (b) R.
This is due to a small Do splitting (Fig. 1). The six H2 Os make the relatively weak s-bonds and hence render the ds orbitals weakly antibonding. Accordingly, the ds orbitals can accommodate extra electrons. In a sense, the water molecules may be regarded as a solvent to stabilize the positive charge of metals. In other words, the solvation stabilization overrides the electronic configurational destabilization. 4) [20]. The si-face of the acrylamide CbC bond forms a p-p stack with the 4-phenyl group of the chiral oxazolidine ligand, and only the re-face is open to the cycloaddition toward cyclopentadiene.