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. 2020 Mar;60(3-4):259-267.
doi: 10.1002/ijch.201900108. Epub 2020 Jan 24.

Pd-Catalyzed C-C, C-N, and C-O Bond-Forming Difunctionalization Reactions of Alkenes Bearing Tethered Aryl/Alkenyl Triflates

Derick R White  1 , Evan C Bornowski  1 , John P Wolfe  1
Affiliations

Pd-Catalyzed C-C, C-N, and C-O Bond-Forming Difunctionalization Reactions of Alkenes Bearing Tethered Aryl/Alkenyl Triflates

Derick R White et al. Isr J Chem. 2020 Mar.

Abstract

Over the past few years our group has described a new type of alkene difunctionalization reaction in which aryl or alkenyl triflates bearing tethered alkenes are coupled with various nucleophiles to afford carbocyclic products. The products are formed in moderate to good chemical yield, with generally high levels of stereoselectivity. Our progress to date in this area, which includes reactions of amine, alcohol, enolate, and indole nucleophiles, is described in this review.

Keywords: Alkenes; Carbocycles; Cross Coupling; Heterocycles; Palladium.

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Figures

Scheme 1.
Scheme 1.
Synthesis of heterocycles
Scheme 2.
Scheme 2.
Planned synthesis of carbocycles
Scheme 3.
Scheme 3.
Preliminary experiments and proof-of-concept
Scheme 4.
Scheme 4.
Optimization of the Enantioselective Reaction
Scheme 5.
Scheme 5.
Enantioselective alkene carboamination reactions
Scheme 6.
Scheme 6.
Carboamination reactions of cyclic alkenyl triflates
Scheme 7.
Scheme 7.
Carboamination reactions of acyclic alkenyl triflates
Scheme 8.
Scheme 8.
Carboalkoxylation reactions of aryl triflates
Scheme 9.
Scheme 9.
Carboalkoxylation reactions of alkenyl triflates
Scheme 10.
Scheme 10.
Reactions of malonates with terminal alkene substrates
Scheme 11.
Scheme 11.
Reactions of malonates with internal alkene substrates
Scheme 12.
Scheme 12.
Reactions of ketone and ester enolates
Scheme 13.
Scheme 13.
Reactions of indole nucleophiles
Scheme 14.
Scheme 14.
Stereochemistry of alkene addition
Scheme 15.
Scheme 15.
Model for enantioselectivity
Scheme 16.
Scheme 16.
Model for diastereoselectivity
See this image and copyright information in PMC

References

    1. :a) Garlets ZJ, White DR, Wolfe JP, Asian. J. Org. Chem 2017, 6, 636.b) Wolfe JP Top. Heterocycl. Chem 2013, 1.c) Schultz DM, Wolfe JP, Synthesis 2012, 44, 351.d) Wolfe JP Synlett 2008, 2913.

    1. :a)Chemler SR, Karyakarte SD, Khoder ZM, J. Org. Chem 2017, 82, 11311.b)Muñiz K, Martinez C, J. Org. Chem 2013, 78, 2168.c)Giri R, KC S, J. Org. Chem 2018, 83, 3013.d)Yin G, Mu X, Liu G, Acc. Chem. Res 2016, 49, 2413.e)Jensen KH, Sigman MS, Org. Biomol. Chem 2008, 6, 4083.

    1. a)Wolfe JP, Rossi MA, J. Am. Chem. Soc 2004, 126, 1620. - PubMed
    2. b)Hay MB, Hardin AR, Wolfe JP, J. Org. Chem 2005, 70, 3099. - PMC - PubMed
    3. c)Hay MB, Wolfe JP, J. Am. Chem. Soc 2005, 127, 16468. - PMC - PubMed
    4. d)Hopkins BA, Garlets ZJ, Wolfe JP, Angew. Chem. Int. Ed 2015, 54, 13390. - PMC - PubMed
    1. Giampietro NC, Wolfe JP, J. Am. Chem. Soc 2008, 130, 12907. - PMC - PubMed
    1. a)Ney JE, Wolfe JP, Angew. Chem. Int. Ed 2004, 43, 3605. - PubMed
    2. b)Bertrand MB, Wolfe JP, Tetrahedron 2005, 61, 6447.
    3. c)Org. Lett 2007, 9, 457.
    4. d)Bertrand MB, Neukom JD, Wolfe JP, J. Org. Chem 2008, 73, 8851. - PMC - PubMed
    5. e)Peterson LJ, Wolfe JP, Adv. Synth. Catal 2015, 357, 2339. - PMC - PubMed