Nozaki-Hiyama-Kishi reaction allylation

Grigg and coworkers developed bimetallic domino reactions such as the electro-chemically driven Pd/Cr Nozaki-Hiyama-Kishi reaction [69], the Pd/In Barbier-type allylation [70], Heck/Tsuji-Trost reaction/1,3 dipolar cycloaddition [71], the Heck reaction/metathesis [72], and several other processes [73-75]. A first example for an anion capture approach, which was performed on solid phase, is the reaction of 6/1-134 and 6/1-135 in the presence of CO and piperidine to give 6/1-136. Liberation from solid phase was achieved with HF, leading to 6/1-137 (Scheme 6/1.30) [76]. 

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]. 

Berkessel, A., Menche, D., Sklorz, C. A., Schroder, M., Paterson, I. A highly enantioselective catalyst for the asymmetric Nozaki-Hiyama-Kishi reaction of allylic and vinylic halides. Arrgew. Chem., Int, Ed, Engl, 2003,42,1032-1035. 

Alkylations. Using Cp2Cr as catalyst together with Mn and MejSiCl to induce the reaction of iodoarenes, iodoalkynes, allyl bromides, and enol triflates to aldehydes, secondary alcohols are formed. This process is a catalytic version of the Nozaki-Hiyama-Kishi reaction. Active Cr(II) catalyst can also be generated by Mn reduction of CpCrClj or CrClj. 

One of the attractive features of the Nozaki-Hiyama-Kishi reaction is that crotyl bromide and other -Y-monosubstituted allylic hahdes usually react with aldehydes to form homoal-lylic alcohols with a high degree of a/jfr-selectivity (Scheme 12.4). This preference for the a fr-product is independent of the double-bond configuration of the starting halide. 

The one-pot Barbier-type addition of alkenyl, aryl, allyl, vinyl, propargyl, alkynyl, or allenylchromium compounds to aldehydes or ketones is known as the Nozaki-Hiyama-Kishi (NHK) reaction. An excellent review by Furstner published in 1999 detailed the exhaustive literature on the carbon-carbon bond formations involving organochromium(III) reagents. This chapter will present major developments and examples of recent carbon-carbon bond formation methodology and improvements as well as their use in natural products synthesis since 1999. 

The catalytic asymmetric allylation of aldehydes is another reaction that has received a great deal of attention. Both allylstannes and the less reactive allylsilanes undergo addition to aldehydes with high ee in the presence of enantiomerically pure Lewis acids and Lewis bases and asymmetric versions of the chromium-catalysed Kishi-Nozaki-Hiyama reaction utilising allyl halides have recently been developed. 

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