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. 2017 Nov 6;56(45):14212-14216.
doi: 10.1002/anie.201706554. Epub 2017 Oct 9.

Visible Light-Induced Room-Temperature Heck Reaction of Functionalized Alkyl Halides with Vinyl Arenes/Heteroarenes

Daria Kurandina  1 , Marvin Parasram  1 , Vladimir Gevorgyan  1
Affiliations

Visible Light-Induced Room-Temperature Heck Reaction of Functionalized Alkyl Halides with Vinyl Arenes/Heteroarenes

Daria Kurandina et al. Angew Chem Int Ed Engl. .

Abstract

The first visible light-induced Pd-catalyzed Heck reaction of α-heteroatom substituted alkyl iodides and -bromides with vinyl arenes/heteroarenes has been developed. This transformation efficiently proceeds at room temperature and enables synthesis of valuable functionalized allylic systems, such as allylic silanes, boronates, germanes, stannanes, pivalates, phosphonates, phthalimides, and tosylates from the corresponding α-substituted methyl iodides. Notably, synthesis of the latter substrates failed under existing thermally induced Pd-catalyzed conditions, which highlights the importance of visible light for this transformation.

Keywords: Heck reaction; alkyl radicals; allylic synthons; palladium; photocatalysis.

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Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Palladium-catalyzed alkyl-Heck reactions.
Scheme 2
Scheme 2
Performed and reported transformations of obtained products. Conditions: a) One-pot reaction: 1) Xantphos Pd G3 (10 mol%), N(iPr)2Et (2.2 equiv), 1d (1.5 equiv), 2i (1 equiv), PhH, blue LED, RT, 12 h. 2) 30% H2O2, THF, RT. b) One-pot reaction: 1) Xantphos Pd G3 (10 mol%), N(iPr)2Et (2.2 equiv), 1d (1.5 equiv), 2a (1 equiv), PhH, blue LED, RT, 12 h. 2) 4-Nitrobenzaldehyde (2 equiv), diphenyl phosphate (2 equiv), PhH, RT, 12 h. c) 3la (1 equiv), 1,1-dimethoxyethane (1.03 equiv), TiCl4 (1.2 equiv), DCM, −78 °C, 15 minutes.
Scheme 3
Scheme 3
Plausible reaction mechanism.
Scheme 4
Scheme 4
Initial mechanistic studies.
See this image and copyright information in PMC

References

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