Nozaki-Hiyama-Kishi conditions

Mohapatra et al. reported on the macrocyclization of intermediate 31 under Nozaki-Hiyama-Kishi conditions (CrCl2, NiCl2, dimethylsulfoxide [DMSO], 85% over two steps). Subsequent deprotection afforded Amphidinolactone A (Scheme 12.30)." ... 

With substrates 82 and 137 in hand, the stage was set for the Nozaki-Hiyama-Kishi reaction it was performed using CrCli and 0.1% NiCh in dry DMSO. Under these mild and chemoselective conditions, a diastereomeric mixture of alcohols 138 was obtained in a 37% yield. Further optimization of these reaction conditions was not investigated due to the small quantity of substrate available. 

Therefore, 42 was directly converted to cw-diene 44 by employing a combination of the Nozaki-Hiyama-Kishi reaction followed by a Peterson elimination employing the conditions described by Paterson. ... 

Pietruszka [75] reported the total synthesis of a series of solandelactones (A-H) by the coupling reaction of the lactone 78, the key intermediate, with side chains 79 and 80 (Scheme 5.27). Lactone 78 was prepared by cyclization of the seco-acid 77 under Yamaguchi conditions in good yield (85%). Finally, the Nozaki-Hiyama-Kishi coupling of the unsaturated lactone aldehyde or its saturated counterpart with the iodide 79 or 80 afforded solandelactones A-H in good yields as separable diastereomeric mixtures (ratio 2 1). 

Pilli and Victor reported on a concise synthesis of (—)-decarestrictine D 32, which uses an intramolecular Nozaki-Hiyama-Kishi reaction as the penultimate step. Aldehyde 33 was prepared via a Dess-Martin oxidation and immediately submitted to NHK conditions of CrCl2-0.5% NiCl2 (15 equiv) in DMF to afford the tert-butyldimethyl-silyl-protected (—)-decarestrictine D 34 (Scheme 12.31). 5-(Z)-7-Oxozeaenol, also known as LL-Z1640-2 35, was isolated in 1978 by McGahren et al. from an unidentified fungus Lederle culture 121640 and has attracted interest as a potent kinase inhibitor (Figure 12.4). ... 

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