FULL PAPERS
anomalous dispersion effects in diffraction measurements on
the crystal. The enantiomer has been assigned by reference
to an unchanging chiral center in the synthetic procedure
(see cif-files for details). Due to the bad quality of the data
of 1a-Br they were not deposited with The Cambridge Crys-
tallographic Data Centre. However, the constitution and ab-
solute configuration was determined reliably (see 2a-Br.cif
and 2a-Br checkcif.pdf for more information).
519; Angew. Chem. Int. Ed. 1986, 25, 508–524; e) J. K.
Stille, Angew. Chem. 1986, 98, 504–519; Angew. Chem.
Int. Ed. 1986, 25, 508.
[5] a) K. Sonogashira, J. Organomet. Chem. 2002, 653, 46–
49; b) K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahe-
dron Lett. 1975, 16, 4467–4470.
[6] a) A. O. King, N. Okukado, E.-i. Negishi, J. Chem. Soc.
Chem. Commun. 1977, 683–684; b) E. Negishi, T. Taka-
hashi, S. Baba, D. E. Van Horn, N. Okukado, J. Am.
Chem. Soc. 1987, 109, 2393–2401.
3b: colourless crystals, C25H34O4, Mr =398.52, crystal size
0.30ꢆ0.16ꢆ0.06 mm, monoclinic, space group P21 (No. 4),
a=11.0356(5) ꢅ, b=7.0949(3) ꢅ, c=13.2814(6) ꢅ, b=
91.549(1)8, V=1039.51(8) ꢅ3, Z=2, 1=1.273 Mg/mÀ3, m(Cu-
Ka)=0.671 mmÀ1, F(000)=432, 2qmax =144.28, 13696 reflec-
tions, of which 4059 were independent (Rint =0.021), 264 pa-
rameters, 1 restraint, R1 =0.028 (for 4011 I> 2s(I)), wR2 =
0.076 (all data), S=1.07, largest diff. peak/hole=0.253/
À0.120 eꢅÀ3, x=À0.06(4), y=À0.05(4).
[7] a) K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem.
Soc. 1972, 94, 4374–4376; b) C. E. I. Knappke, A. Jaco-
bi von Wangelin, Chem. Soc. Rev. 2011, 40, 4948–4962.
[8] a) D. Czajkowska-Szczykowska, J. W. Morzycki, A.
Wojtkielewicz, Steroids 2015, 97, 13–44; b) R. Skoda-
Fçldes, L. Kollꢇr, Chem. Rev. 2003, 103, 4095–4130.
[9] a) A. Arcadi, A. Burini, S. Cacchi, M. Delmastro, F.
Marinelli, B. Pietroni, Synlett 1990, 1990, 47–48; b) A.
Arcadi, S. Cacchi, M. Del Rosario, G. Fabrizi, F. Ma-
rinelli, J. Org. Chem. 1996, 61, 9280–9288; c) S. Cacchi,
E. Morera, G. Ortar, Tetrahedron Lett. 1984, 25, 2271–
2274; d) R. Skoda-Fçldes, L. Kollꢇr, F. Marinelli, A.
Arcadi, Steroids 1994, 59, 691–695.
[10] a) P. G. Ciattini, E. Morera, G. Ortar, Tetrahedron Lett.
1990, 31, 1889–1892; b) G. A. Potter, S. E. Barrie, M.
Jarman, M. G. Rowlands, J. Med. Chem. 1995, 38,
2463–2471; c) J. Chao, Y. Ling, X. Liu, X. Luo,
A. M. H. Brodie, Steroids 2006, 71, 585–590; d) Q. Sun,
C. Jiang, H. Xu, Z. Zhang, L. Liu, C. Wang, Steroids
2010, 75, 936–943.
6a: colourless crystals, C26H36O2, Mr =380.55, crystal size
0.20ꢆ0.12ꢆ0.06 mm, orthorhombic, space group P212121
(No.
19),
a=5.7932(3) ꢅ,
b=12.4890(7) ꢅ,
c=
29.5589(17) ꢅ, V=2138.6(2) ꢅ3, Z=4, 1=1.182 Mg/mÀ3,
m(Cu-Ka)=0.555 mmÀ1, F(000)=832, 2qmax =144.08, 20419
reflections, of which 4195 were independent (Rint =0.019),
257 parameters, 1 restraint, R1 =0.032 (for 4138 I> 2s(I)),
wR2 =0.085 (all data), S=1.02, largest diff. peak/hole=
0.234/À0.172 eꢅÀ3, x=À0.09(4), y=À0.08(4).
CCDC 1511909 (3b), CCDC 1511910 (5a), CCDC
1511911 (6a), CCDC 1521243 (9a) and CCDC 1511912
(11b) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via
of the data of 1a-Br the data were not deposited with The
Cambridge Crystallographic Data Centre.
[11] a) N. G. Aher, R. G. Gonnade, V. S. Pore, Synlett 2009,
2009, 2005–2009; b) M. Bꢈrubꢈ, D. Poirier, Org. Lett.
2004, 6, 3127–3130.
[12] a) B. M. Trost, J. Dumas, J. Am. Chem. Soc. 1992, 114,
1924–1925; b) B. M. Trost, J. Dumas, M. Villa, J. Am.
Chem. Soc. 1992, 114, 9836–9845; c) L. F. Tietze, J. M.
Wiegand, C. Vock, J. Organomet. Chem. 2003, 687,
346–352; d) P. Lacrouts, P. J. Parsons, C. S. Penkett,
A. R. Raza, Synlett 2005, 2005, 2767–2768.
Acknowledgements
V.K. gratefully acknowledges the Studienstiftung des deut-
schen Volkes for financial support.
[13] a) H. Renata, Q. Zhou, P. S. Baran, Science 2013, 339,
59–63; b) H. Renata, Q. Zhou, G. Dꢂnstl, J. Felding,
R. R. Merchant, C.-H. Yeh, P. S. Baran, J. Am. Chem.
Soc. 2015, 137, 1330–1340; c) R. A. Shenvi, C. A. Guer-
rero, J. Shi, C.-C. Li, P. S. Baran, J. Am. Chem. Soc.
2008, 130, 7241–7243; d) J. Shi, G. Manolikakes, C.-H.
Yeh, C. A. Guerrero, R. A. Shenvi, H. Shigehisa, P. S.
Baran, J. Am. Chem. Soc. 2011, 133, 8014–8027;
e) K. C. Nicolaou, X.-S. Peng, Y.-P. Sun, D. Polet, B.
Zou, C. S. Lim, D. Y. K. Chen, J. Am. Chem. Soc. 2009,
131, 10587–10597; f) K. C. Nicolaou, Y.-P. Sun, X.-S.
Peng, D. Polet, D. Y. K. Chen, Angew. Chem. 2008, 120,
7420–7423; Angew. Chem. Int. Ed. 2008, 47, 7310–7313;
g) M. Honma, M. Nakada, Tetrahedron Lett. 2007, 48,
1541–1544; h) G. Stork, F. West, H. Y. Lee, R. C. A.
Isaacs, S. Manabe, J. Am. Chem. Soc. 1996, 118, 10660–
10661; i) L.-H. Kuo, H.-P. Fang, M.-F. Wu, Y.-S. Chang,
(Scinopharm Taiwan, Ltd., USA), U.S. Patent, 14/
315642, 2014.
References
[1] K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem.
2005, 117, 4516–4563; Angew. Chem. Int. Ed. 2005, 44,
4442–4489.
[2] a) I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000,
100, 3009–3066; b) A. B. Dounay, L. E. Overman,
Chem. Rev. 2003, 103, 2945–2964; c) R. F. Heck, Acc.
Chem. Res. 1979, 12, 146–151; d) R. F. Heck, J. P.
Nolley, J. Org. Chem. 1972, 37, 2320–2322.
[3] a) N. Miyaura, A. Suzuki, J. Chem. Soc. Chem.
Commun. 1979, 866–867; b) N. Miyaura, A. Suzuki,
Chem. Rev. 1995, 95, 2457–2483; c) N. Miyaura, K.
Yamada, A. Suzuki, Tetrahedron Lett. 1979, 20, 3437–
3440; d) A. Suzuki, Acc. Chem. Res. 1982, 15, 178–184.
[4] a) V. Farina, V. Krishnamurthy, W. J. Scott, in: Organic
Reactions, John Wiley & Sons, Inc. 2004; b) D. Milstein,
J. K. Stille, J. Am. Chem. Soc. 1978, 100, 3636–3638;
c) D. Milstein, J. K. Stille, J. Am. Chem. Soc. 1979, 101,
4992–4998; d) J. K. Stille, Angew. Chem. 1986, 98, 504–
[14] a) D. H. R. Barton, R. E. OꢃBrien, S. Sternhell, J.
Chem. Soc. 1962, 470–476; b) H. Mori, K. Tsuneda,
Chem. Pharm. Bull. 1963, 11, 1413–1417.
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