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. 2017 Apr 7;19(7):1527-1529.
doi: 10.1021/acs.orglett.7b00449. Epub 2017 Mar 14.

Enantioselective Iridium-Catalyzed Allylic Alkylation Reactions of Masked Acyl Cyanide Equivalents

J Caleb Hethcox  1 , Samantha E Shockley  1 , Brian M Stoltz  1
Affiliations

Enantioselective Iridium-Catalyzed Allylic Alkylation Reactions of Masked Acyl Cyanide Equivalents

J Caleb Hethcox et al. Org Lett. .

Abstract

The first enantioselective iridium-catalyzed allylic alkylation reaction of a masked acyl cyanide (MAC) reagent has been developed. The transformation allows for the use of an umpoled synthon, which serves as a carbon monoxide equivalent. The reaction proceeds with good yield and excellent selectivity up to gram scale for a wide range of substituted allylic electrophiles, delivering products amenable to the synthesis of highly desirable, enantioenriched vinylated α-aryl carbonyl derivatives.

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Figures

Figure 1
Figure 1
Iridium-catalyzed allylic alkylation strategies.
Scheme 1
Scheme 1. Electrophile Substrate Scopea
aReactions performed on 0.2 mmol scale. bIsolated yield. cDetermined by chiral HPLC or SFC analysis. dReaction run for 36 h at 50 °C.
Scheme 2
Scheme 2. Preparatory Scale Reaction
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References

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    1. For selected reviews of asymmetric iridium-catalyzed allylic alkylation, see: Helmchen G, Dahnz A, Dubon P, Schelwies M, Weihofen R. Chem Commun. 2007:675–691.Hartwig JF, Pouy MJ. Top Organomet Chem. 2011;34:169–208.Liu WB, Xia JB, You SL. Top Organomet Chem. 2011;38:155–208.Hethcox JC, Shockley SE, Stoltz BM. ACS Catal. 2016;6:6207–6213.

    1. Nucleophilic additions of methylene imines to iridium π-allyl complexes have been accomplished via an umpoled strategy. However, the products delivered resemble products of standard iridium-catalyzed allylic alkylation of enolates; see: Su YL, Li YH, Chen YG, Han ZY. Chem Commun. 2017;53:1985–1988.

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