Nozaki-Hiyama allylation

Inoue, M., Suzuki, T., Nakada, M. Asymmetric Catalysis of Nozaki-Hiyama Allylation and Methallylation with A New Tridentate Bis(oxazolinyl)carbazole Ligand. J. Am. Chem. Soc. 2003,125, 1140-1141. 

Suzuki, T., Kinoshita, A., Kawada, H., Nakada, M. A new asymmetric tridentate carbazole ligand Its preparation and application to Nozaki-Hiyama allylation. Synlett 2003, 570-572. 

Asymmetric Nozaki-Hiyama allylation of benzaldehyde with a multidentate proline-derived amino alcohol ligand 13 showed good enantioselectivity up... 

Mioskowski and Flack showed that (Z)-2-chloroalk-2-en-l-ols 42 were obtained in excellent yields from a wide variety of aldehydes by addition of ( )-chromium vinylidene carbenoids 41, generated from trichloroalkanes 40 with CrCl2 in THF at room temperature. The same authors also reported CrCh-mediated condensations of x-chloro-gew-trichloroalkanes with aldehydes to give homolallyic alcohols through a hydride rearrangement followed by a Nozaki-Hiyama allylation. ... 

McManus HA, Cozzi P-G, Guiry PJ. Application of tridentate bis(oxazoline) ligands in catalytic asymmetric Nozaki-Hiyama allylation and crotylation an example of high enan-tioselection with a non-symmetric bis(oxazoline) ligand. Adv. Synth. Catal. 2006 348 551-558. 

Xia G, Yamamoto H. Catalytic enantioselective Nozaki-Hiyama allylation reaction with tethered bis(8-quinolinolato) (TBOx) chromium complex. J. Am. Chem. Soc. 2006 128 2554-2555. 

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]. 

Nozaki-Hiyama-Kishi (NHK) reactions215,216 are well known and often employed as a useful method for the synthesis of natural products by coupling of allyl, alkenyl, alkynyl, and aryl halides or triflates with aldehydes. The organochromium reagents are prepared from the corresponding halides or triflates and chromium(ll) chloride, and are employed in polar aprotic solvents (THF, DMF, DMSO, etc.). Subsequently, it was found that nickel salts exhibited a significant catalytic effect on the formation of the C-Cr bond217,218 (Equation (19)). 

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. 

Cyclic enediynes have been obtained also by elimination of a suitable propargylic alcohol on a preformed cyclic diyne.5 An example is shown in Scheme 19.7, where the cyclization was accomplished through a Nozaki-Hiyama intramolecular allyl bromide addition to an aldehyde.5 This method proved successful for the synthesis of a particular enediyne that, because of conformational biases, could not be obtained by the strategies described above. 

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. 

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. 

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