Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2009;48(17):3146-9.
doi: 10.1002/anie.200900218.

Palladium-catalyzed oxidative intermolecular difunctionalization of terminal alkenes with organostannanes and molecular oxygen

Kaveri Balan Urkalan  1 , Matthew S Sigman
Affiliations

Palladium-catalyzed oxidative intermolecular difunctionalization of terminal alkenes with organostannanes and molecular oxygen

Kaveri Balan Urkalan et al. Angew Chem Int Ed Engl. 2009.

Abstract

A cationic palladium complex catalyzes the title transformations, which are thought to proceed via a pi-allyl or pi-benzyl intermediate. The regioselectivity of the reaction (1,2- or 1,1-difunctionalization) depends on the type of terminal double bond (conjugated or nonconjugated) in the substrate (see scheme) and appears to be controlled by the relative rates of beta-hydride elimination and transmetalation. DMA=dimethylacetamide, Tf=triflyl.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Proposed mechanism for the oxidative Heck reaction (a) and interception of the σ-alkyl palladium(II) intermediate by transmetalation (b).
Figure 1
Figure 1
1,2-Diarylation versus 1,1-diarylation of styrenes and resulting Hammett analysis.
Scheme 2
Scheme 2
1,1-Diarylation of terminal alkenes (a) and related mechanistic experiments (b).
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. For reviews of the Heck reaction, see: Heck RF. Org. React. 1982;27:345–390.; Beletskaya IP, Cheprakov AV. Chem. Rev. 2000;100:3009–3066.; Whitcombe NJ, Hii KK, Gibson SE. Tetrahedron. 2001;57:7449–7476.; Kondolff I, Doucet H, Santelli M. Tetrahedron Lett. 2003;44:8487–8491.

    1. For examples of oxidative Heck reactions, see: Du X, Suguro M, Hirabayashi K, Mori A, Nishikata T, Hagiwara N, Kawata K, Okeda T, Wang HF, Fugami K, Kosugi M. Org. Lett. 2001;3:3313–3316.; Parrish JP, Jung YC, Shin SI, Jung KW. J. Org. Chem. 2002;67:7127–7130.; Jung YC, Mishra RK, Yoon CH, Jung KW. Org. Lett. 2003;5:2231–2234.; Andappan MMS, Nilsson P, von Schenck H, Larhed M. J. Org. Chem. 2004;69:5212–5218.; Yoo KS, Yoon CH, Jung KW. J. Am. Chem. Soc. 2006;128:16384–16393.; Delcamp JH, Brucks AP, White MC. J. Am. Chem. Soc. 2008;130:11270–11271.; for an example in which oxygen and base-free conditions are used, see: Ruan J, Li X, Saidi O, Xiao J. J. Am. Chem. Soc. 2008;130:2424–2425.

    1. Organ MG, Chass GA, Fang DC, Hopkinson AC, Valentea C. Synthesis. 2008:2776–2797.

    1. For an overview of alkene difunctionalization reactions under palladium catalysis, see: Jensen KH, Sigman MS. Org. Biomol. Chem. 2008;6:4083–4088.; for examples of alkene diamination, see: Muniz K, Hovelmann CH, Streuff J. J. Am. Chem. Soc. 2008;130:763–773.; Muniz K, Streuff J, Hovelmann CH, Nunez A. Angew. Chem. 2007;119:7255–7258.; Angew. Chem. Int. Ed. 2007;46:7125–7127.; for an example of aminooxygenation, see: Desai LV, Melanie SS. Angew. Chem. 2007;119:5839–5842.; Angew. Chem. Int. Ed. 2007;46:5737–5740.; for an example of aminoacetoxylation, see: Liu G, Stahl SS. J. Am. Chem. Soc. 2006;128:7179–7181.

    1. Kalyani D, Sanford MS. J. Am. Chem. Soc. 2008;130:2150–2151. - PubMed

Publication types