SN2-Selective allylic substitution of chiral γ-aryl substituted allylic picolinates with alkynylcopper reagents

Tetrahedron Letters

Volumn 51, Issue 42, 2010, Pages 5592-5595

  Wang, Qian ^a   Kobayashi, Yuichi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Acetylene; Allylic substitution; CH 2Cl2; Picolinate; Solvent effect

Indexed keywords

ACETYLENE; ALKYNYL GROUP; ALLYL COMPOUND; BROMINE DERIVATIVE; COPPER COMPLEX; METHYL GROUP; PHENYL GROUP; PICOLINIC ACID DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; REAGENT;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; CONJUGATION; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; REACTION ANALYSIS; SOLVENT EFFECT; STEREOCHEMISTRY; SYNTHESIS;

EID: 77956647531     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2010.08.051     Document Type: Article

References (30)

1. C.A. Falciola, and A. Alexakis Eur. J. Org. Chem. 2008 3765 3780
2. A. Kar, and N.P. Argade Synthesis 2005 2995 3022
3. E. Negishi, and F. Liu F. Diederich, P.J. Stang, Metal-catalyzed Cross-coupling Reactions 1998 Wiley-VCH Weinheim Chapter 1
4. H.L. Goering, and S.S. Kantner J. Org. Chem. 46 1981 2144 2148
5. H.L. Goering, E.P. Seitz Jr., and C.C. Tseng J. Org. Chem. 46 1981 5304 5308 and references cited therein
6. Cf. substitution of γ-aryl primary allylic esters and halides: S. Okamoto, S. Tominaga, N. Saino, K. Kase, and K. Shimoda J. Organomet. Chem. 690 2005 6001 6007
7. C.A. Falciola, K. Tissot-Croset, and A. Alexakis Angew. Chem., Int. Ed. 45 2006 5995 5998
8. C.A. Falciola, K. Tissot-Croset, H. Reyneri, and A. Alexakis Adv. Synth. Catal. 350 2008 1090 1100 and references cited therein
9. H.L. Goering, and C.C. Tseng J. Org. Chem. 48 1983 3986 3990
10. C.C. Tseng, S.-J. Yen, and H.L. Goering J. Org. Chem. 51 1986 2892 2895
11. J. Norinder, K. Bogár, L. Kanupp, and J.-E. Bäckvall Org. Lett. 9 2007 5095 5098
12. Y. Takashima, and Y. Kobayashi J. Org. Chem. 74 2009 5920 5926
13. Defined as '(% ee of product/% ee of substrate) × 100'.
14. Y. Kiyotsuka, H.P. Acharya, Y. Katayama, T. Hyodo, and Y. Kobayashi Org. Lett. 10 2008 1719 1722
15. Y. Kiyotsuka, and Y. Kobayashi Tetrahedron Lett. 49 2008 7256 7259
16. Y. Kiyotsuka, Y. Katayama, H.P. Acharya, T. Hyodo, and Y. Kobayashi J. Org. Chem. 74 2009 1939 1951
17. T. Hyodo, Y. Kiyotsuka, and Y. Kobayashi Org. Lett. 11 2009 1103 1106
18. Y. Kiyotsuka, and Y. Kobayashi Tetrahedron 66 2010 676 684
19. Y. Kiyotsuka, and Y. Kobayashi J. Org. Chem. 74 2009 7489 7495
20. H. Chen, and M.-Z. Deng J. Organomet. Chem. 603 2000 189 193
21. 2 than that in THF, thus promoting the reaction at the α carbon.
22. 2 and toluene: E.S.M. Persson, M. Van Klaveren, D.M. Grove, J.E. Bäckvall, and G. Van Koten Chem. Eur. J. 1 1995 351 359
23. A. Alexakis, C. Malan, L. Lea, C. Benhaim, and X. Fournioux Synlett 2001 927 930
24. J.L. Belelie, and J.M. Chong J. Org. Chem. 67 2002 3000 3006
25. CuX-based reagents (X = Br, CN) gave low selectivity in reactions of other combination of substrate/reagents.
26. K. Matsumura, S. Hashiguchi, T. Ikariya, and R. Noyori J. Am. Chem. Soc. 119 1997 8738 8739
27. Hydrogenation by using 10%Pd/C in solvents such as EtOAc suffered from a partial racemization.
28. D.D. Davis, and G.G. Ansari J. Org. Chem. 35 1970 4285 4287
29. 4 probably assists partial racemization during the substitution reaction.
30. R/min = 20.4 (S-isomer, major), 24.2 (R-isomer, minor).