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DFT studies on the palladium-catalyzed dearomatization reaction between naphthalene allyl chloride and allyltributylstannane

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Abstract

The Pd-catalyzed dearomatization of naphthalene allyl chloride with allyltributylstannane has been investigated using density functional theory (DFT) calculations at the B3LYP level. The calculations indicate that the (ŋ 1-allyl)(ŋ 3-allyl)Pd(PH3) complex is responsible for the formation of ortho-dearomatized product. Moreover it is easy to produce the ortho-dearomatized product when reductive elimination starts from (ŋ 3-allylnaphthalene)(ŋ 1-allyl)Pd complex 7, while it is easy to form the para-dearomatized product when reductive elimination starts from (ŋ 3-allylnaphthalene)(ŋ 1-allyl)Pd complex 9. The Stille coupling products can’t be produced due to high reaction energy barrier.

Two mechanisms of dearomatization are investigated by DFT, and (ŋ 1-allyl)(ŋ 3-allyl)Pd(PH3) complexes are the main intermediates for ortho-dearomatized product.

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Acknowledgments

This work was supported by the National Science Foundation of China (21001019) the Fundamental Research Funds for the Central Universities (DUT15LK24). The results were obtained on the ScGrid of Supercomputing Center, Computer Network Information Center of Chinese Academy of Sciences.

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Authors and Affiliations

  1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China

    Wei Cao, Dongxu Tian & Dongxue Han

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  1. Wei Cao
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  2. Dongxu Tian
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  3. Dongxue Han
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Correspondence to Dongxu Tian.

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Cao, W., Tian, D. & Han, D. DFT studies on the palladium-catalyzed dearomatization reaction between naphthalene allyl chloride and allyltributylstannane. J Mol Model 21, 260 (2015). https://doi.org/10.1007/s00894-015-2802-2

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