Intramolecular Nozaki-Hiyama-Kishi reaction

Example 3, Intramolecular Nozaki-Hiyama-Kishi reaction ... 

Scheme 3.13 Protecting-group directed stereoselective intramolecular Nozaki-Hiyama-Kishi reaction. A concise and efficient total synthesis of amophidinolactone A.

Scheme 3.14 Stereoselectivity in the intramolecular Nozaki-Hiyama-Kishi reaction influence of the substitution pattern and protecting groups in the construction of 10-membered lactones.

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). ... 

Mohapatra DK, Das PP, Pattanayak R, Gayatri G, Sastry GN, Yadav, JS. Protecting-group directed stereoselective intramolecular Nozaki-Hiyama-Kishi reactions a concise and efficient synthesis of Amphidinolactone A. Eur. J. Org. Chem. 2010 4775 784. 

Pilli RA, Victor MM. Total synthesis of (—)-Decarestrictine D through a stereoselective intramolecular Nozaki-Hiyama-Kishi reaction. Tetrahedron Lett. 1998 39 4421 1424. 

Many catalytic reactions are not sensitive to the presence of a sulfur atom on the substrate. Two examples can be quoted the Nozaki-Hiyama-Kishi reaction where a chlorosilane-mediated Cr-Mn-catalyzed C-C coupling occurs between a halogenoalkene and an aldehyde [63], and the [IrCl(CO)3]-catalyzed intramolecular allyl transfer in functionalized 1,3-thiozanes [64]. 

The first total synthesis of pinnatoxin A (104) was completed by Kishi s group in 1998 [67,68]. Their synthetic strategy is shown in Scheme 13. They planned to make the seven-membered iminium ring at the last stage, and the key macrocyclization was carried out by an intramolecular Diels-Alder reaction. Fragments 138-141 were coupled using the Nozaki-Hiyama-Kishi reaction, Juba coupling reaction etc. 

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