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. 2010 Apr 7;132(13):4562-3.
doi: 10.1021/ja100949e.

anti-Diastereo- and enantioselective carbonyl (hydroxymethyl)allylation from the alcohol or aldehyde oxidation level: allyl carbonates as allylmetal surrogates

Yong Jian Zhang  1 , Jin Haek Yang, Sang Hoon Kim, Michael J Krische
Affiliations

anti-Diastereo- and enantioselective carbonyl (hydroxymethyl)allylation from the alcohol or aldehyde oxidation level: allyl carbonates as allylmetal surrogates

Yong Jian Zhang et al. J Am Chem Soc. .

Abstract

Enantioselective transfer hydrogenation of carbonate 1a in the presence of aromatic, allylic, or aliphatic alcohols 2a-2i employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, 4-cyano-3-nitrobenzoic acid and (S)-SEGPHOS delivers products of (hydroxymethyl)allylation 4a-4i in good isolated yields (60-74%), good anti-diastereoselectivities (5:1-10:1 dr) and exceptional levels of enantiocontrol (93-99% ee). Under identical reaction conditions, but in the presence of isopropanol, aldehydes 3a-3i are converted to an equivalent set of adducts 4a-4i in good isolated yields (58-74%), good anti-diastereoselectivities (4:1-14:1 dr), and exceptional levels of enantiocontrol (95-99% ee). Thus, identical sets of adducts 4a-4i are produced with equal facility from the alcohol or aldehyde oxidation level. These studies represent the first general method for enantioselective carbonyl (hydroxymethyl)allylation, a process that has no highly stereoselective counterpart in conventional allylmetal chemistry.

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Figures

Scheme 1
Scheme 1
Conversion of diol 4c to compounds 5c, 6c and 7c.a aReagents: (a) NaH, TsCl, THF, 82%. (b) n-BuLi, THF, 92%. (c) NaH, H2C=CHCH2Br, THF, 82%. (d) Grubbs I, DCM, 90%. (e) TBSCl, Et3N, DMAP, DCM, 88%. (f) NaH, H2C=CHCH2Br, THF, 90%. (g) Grubbs I, DCM, 91%. See Supporting Information for further details.
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References

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