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. 2012 Jul 20;14(14):3796-9.
doi: 10.1021/ol301681z. Epub 2012 Jul 3.

Iron-catalyzed alkylations of aryl sulfamates and carbamates

Amanda L Silberstein  1 , Stephen D Ramgren, Neil K Garg
Affiliations

Iron-catalyzed alkylations of aryl sulfamates and carbamates

Amanda L Silberstein et al. Org Lett. .

Abstract

The alkylation of aryl sulfamates and carbamates using iron catalysis is reported. The method constructs sp(2)-sp(3) carbon-carbon bonds and provides synthetically useful yields across a range of substrates (>35 examples). The directing group ability of sulfamates and carbamates, accompanied by their low reactivity toward conventional cross-couplings, renders these substrates useful for the synthesis of polyfunctionalized arenes.

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Figures

Figure 1
Figure 1
Iron-catalyzed alkylation of aryl sulfamates and carbamates.
Figure 2
Figure 2
Optimal result obtained after extensive optimization.
Figure 3
Figure 3
Sequential site-selective couplings and assembly of 7.
See this image and copyright information in PMC

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    1. For the iron-catalyzed alkylation of aryl halides, tosylates, and triflates, see: Fürstner A, Leitner A. Angew. Chem. Int. Ed. 2002;41:609. Fürstner A, Leitner A, Méndez M, Krause H. J. Am. Chem. Soc. 2002;124:13856. Fürstner A, Martin R, Krause H, Günter S, Goddard R, Lehmann CW. J. Am. Chem. Soc. 2008;130:8773. For the iron-catalyzed alkylation of heteroaromatic sulfonates and phosphates, see: Gøgsig TM, Lindhardt AT, Skrydstrup T. Org. Lett. 2009;11:4886. For a relevant mechanistic study, see: Kleimark J, Larsson P-F, Emamy P, Hedström A, Norrby P-O. Adv. Synth. Catal. 2012;354:448.

    1. For the related iron-catalyzed alkylation of styrenyl or electrondeficient vinyl pivalates, see: Li B-J, Xu L, Wu Z-H, Guan B-T, Sun C-L, Wang B-Q, Shi Z-J. J. Am. Chem. Soc. 2009;131:14656.

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