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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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