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Highly stereoselective synthesis of (Z)- and (E)-chloro-substituted-\(\alpha \)-methylene-\(\gamma \)-butyrolactone by possibly controlling cis- and trans-chloropalladation

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Abstract

A palladium-catalyzed selective synthesis of cis- or trans-chloro-substituted-\(\alpha \)-methylene-\(\gamma \)-butyrolactones from single substrate (propiolic acid) has been realized by controlling cis- or trans-chloropalladation. This method is highly effective for building C–Cl, C–O, and C–C bonds into a one-pot procedure because of its good atom and step efficiency.

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References

  1. Seechurn CCCJ, Kitching MO, Colacot TJ, Snieckus V (2012) Palladium-catalyzed cross-coupling: a historical contextual perspective to the 2010 Nobel Prize. Angew Chem Int Ed 51:5062–5085. doi:10.1002/anie.201107017

    Article  Google Scholar 

  2. Cacchi S, Fabrizi G (2011) Update 1 of: Synthesis and functionalization of indoles through palladium-catalyzed reactions. Chem Rev 111: PR215–PR283. doi:10.1021/cr100403z

  3. Lyons TW, Sanford MS (2010) Palladium-catalyzed ligand-directed C–H functionalization reactions. Chem Rev 110:1147–1169. doi:10.1021/cr900184e

    Article  PubMed  CAS  Google Scholar 

  4. Muñiz K (2009) High-oxidation-state palladium catalysis: new reactivity for organic synthesis. Angew Chem Int Ed 48:9412–9423. doi:10.1002/anie.200903671

    Article  Google Scholar 

  5. Beccalli EM, Broggini G, Martinelli M, Sottocornola S (2007) C–C, C–O, C–N bond formation on \(\text{ sp}^{2}\) carbon by Pd(II)-catalyzed reactions involving oxidant agents. Chem Rev 107:5318–5365. doi:10.1021/cr068006f

    Google Scholar 

  6. Nicolaou KC, Bulger PG, Sarlah D (2005) Palladium-catalyzed cross-coupling reactions in total synthesis. Angew Chem Int Ed 44:4442–4489. doi:10.1002/anie.200500368

    Article  CAS  Google Scholar 

  7. Chemler SR, Trauner D, Danishefsky SJ (2001) The \(B\)-alkyl suzuki-miyaura cross-coupling reaction: development, mechanistic study, and applications in natural product synthesis. Angew Chem Int Ed 40:4544–4568. doi:10.1002/1521-3773(20011217)

  8. Lu X (2002) Handbook of organopalladium chemistry for organic synthesis, Vol 2, Negishi E (ed). Wiley, New York, pp 2267–2287

  9. Kitson RRA, Millemaggi A, Taylor RJK (2009) The renaissance of \(\alpha \)-methylene-\(\gamma \)-butyrolactones: New synthetic approaches. Angew Chem Int Ed 48:9426–9451 and references therein. doi:10.1002/anie.200903108

  10. Takenaka K, Hashimoto S, Takizawa S, Sasai H (2011) Chlorinative cyclization of 1,6-enynes by enantioselective palladium(II)/palladium(IV) catalysis. Adv Synth Catal 353: 1067–1070. doi:10.1002/adsc.201000926

    Google Scholar 

  11. Li Y, Jardine KJ, Tan R, Song D, Dong VM (2009) Palladium-catalyzed intramolecular carboesterification of olefins. Angew Chem Int Ed 48:9690–9692. doi:10.1002/anie.200905478

    Article  CAS  Google Scholar 

  12. Yin G, Liu G (2008) Palladium-catalyzed oxidative cyclization of enynes with hydrogen peroxide as the oxidant. Angew Chem Int Ed 47:5442–5445. doi:10.1002/anie.200801438

    Article  CAS  Google Scholar 

  13. Li W, shi M (2008) An efficient method for the synthesis of vinylbromohydrin and vinylbromoalkoxy derivatives and cyclocarbonylation of \(\alpha \)-allenic alcohols catalyzed by palladium chloride. J Org Chem 73:6698–6705. doi: 10.1021/jo8009352

    Article  PubMed  CAS  Google Scholar 

  14. Song J, Shen Q, Xu F, Lu X (2007) Cationic Pd(II)-catalyzed enantioselective cyclization of aroylmethyl 2-alkynoates initiated by carbopalladation of alkynes with arylboronic acids. Org Lett 9:2947–2950. doi:10.1021/ol0711772

    Article  PubMed  CAS  Google Scholar 

  15. Yonehara K, Miyoshi Y, Tsukajima A, Akatsuka T, Saito M (2011) Palladium(II)-catalyzed aerobic intermolecular cyclization of acrylic acid with alkenes to \(\alpha \)-methylene-\(\gamma \)-butyrolactones. Adv Synth Catal 353:1071–1075. doi:10.1002/adsc.201100006

  16. Arcadi A, Cacchi S, Fabrizi G, Moro L (1999) Palladium-catalyzed cyclocarbonylation of \(o\)-ethynylphenols and vinyl triflates to form 3-alkylidene-2-coumaranones. Eur J Org Chem 5:1137–1141. doi:10.1002/(SICI)1099-0690(199905)

    Google Scholar 

  17. Huang L, Wang Q, Liu X, Jiang H (2012) Switch of selectivity in the synthesis of \(\alpha \)-methylene-\(\gamma \)-lactones: palladium-catalyzed intermolecular carboesterification of alkenes with alkynes. Angew Chem Int Ed 51:5696–5700. doi: 10.1002/anie.201109141

    Article  CAS  Google Scholar 

  18. Borsini E, Broggini G, Fasana A, Galli S, Khansaa M, Piarulli U, Rigamonti M (2011) Intramolecular palladium-catalyzed aminocarboxylation of olefins as a direct route to bicyclic oxazolidinones. Adv Synth Catal 353:985–994. doi:10.1002/adsc.201000889

    Google Scholar 

  19. Broggini G, Barbera V, Beccalli E, Borsini E, Galli S, Lanza G, Zecchi G (2012) Palladium(II)/copper halide/solvent combination for selective intramolecular domino reactions of indolecarboxylic acid allylamides: An Unprecedented arylation/esterification sequence. Adv Synth Catal 354:159–170. doi:10.1002/adsc.201100614

    Google Scholar 

  20. Kubizna P, Špánik I, Kožíšek J, Szolcsányi P (2010) Synthesis of 2,6-disubstituted piperidine alkaloids from ladybird beetles Calvia 10-guttata and Calvia 14-guttata. Tetrahedron 66: 2351–2355. doi:10.1016/j.tet.2010.01.106

    Google Scholar 

  21. Szolcsányi P, Gracza T, Špánik I (2008) Short racemic syntheses of calvine and epicalvine. Tetrahedron Lett 49:1357–1360. doi:10.1016/j.tetlet.2007.12.099

    Google Scholar 

  22. The structures of these two isomers were identified with \(^{1}\text{ H}\) NMR, \(^{13}\text{ C}\) NMR and HRMs data

  23. Bäckvall J-E, Nilsson YIM, Gatti RGP (1995) Stereochemistry and Mechanism of Chloropalladation of Acetylenes. Organometallics 14:4242–4246. doi:10.1021/om00009a029

    Article  Google Scholar 

  24. Chang S-T, Wang DS-Y, Wu C-L, Shiah S-G, Kuo Y-H, Chang C-J (2000) Cytotoxicity of extractives from Taiwania cryptomerioides heartwood. Phytochemistry 55:227–232. doi:10.1016/S0031-9422(00)00275-2

    Google Scholar 

  25. Novák P, Correa A, Gallardo-Donaire J, Martin R (2011) Synergistic palladium-catalyzed C(sp3)-H activation/C(sp3)-O bond formation: a direct, step-economical route to benzolactones. Angew Chem Int Ed 50:12236–12239. doi:10.1002/anie.201105894

    Article  Google Scholar 

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Acknowledgments

We acknowledge Bo Liu and Tongxiang Cao for their assistance in preparation of intermediates. This research is supported financially by the joint grant of National Natural Science Foundation of China (NSFC) and National Institute of Health (NIH) of USA (No. 81161120402) and the National 863 Program of China, No. 2012AA020303.

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Authors and Affiliations

  1. Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, 2 Nanwei Rd., Xicheng Dist., Beijing,  100050, People’s Republic of China

    Yi Dong, Xiaoyong Guo & Gang Liu

  2. Tsinghua-Peking Center for Life Sciences, Beijing, People’s Republic of China

    Gang Liu

  3. Department of Pharmacology and Pharmaceutical Sciences, School of Medicine, Tsinghua University, Haidian Dist., Beijing,  100084, People’s Republic of China

    YuanYuan Yu & Gang Liu

Authors
  1. Yi Dong
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  2. Xiaoyong Guo
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  3. YuanYuan Yu
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  4. Gang Liu
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Correspondence to Gang Liu.

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Dong, Y., Guo, X., Yu, Y. et al. Highly stereoselective synthesis of (Z)- and (E)-chloro-substituted-\(\alpha \)-methylene-\(\gamma \)-butyrolactone by possibly controlling cis- and trans-chloropalladation. Mol Divers 17, 1–7 (2013). https://doi.org/10.1007/s11030-012-9419-5

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