Chemistry - A European Journal
10.1002/chem.201900564
COMMUNICATION
[
[
[
19] G. Hernández-Torres, A. Urbano, M. C. Carreno, F. Colobert, Org. Lett.
Keywords: C-C bond activation
•
desymmetrization
•
2
009, 11, 4930-4933.
20] V. S. Enev, H. Kaehlig, J. Mulzer, J. Am. Chem. Soc. 2001, 123,
0764-10765;
asymmetric catalysis • iridium catalysis • hydrogenation • enyne
metathesis • cross metathesis
1
21] F. Kleinbeck, G. J. Fettes, L. D. Fader, E. M. Carreira, Chem. Eur. J.
2012, 18, 3598-3610.
[
1]
M. Eggersdorfer, D. Laudert, U. Létinois, T. McClymont, J. Medlock, T.
Netscher, W. Bonrath, Angew. Chem. 2012, 124, 13134-13165.
[22] K. Voigtritter, S. Ghorai, B. H. Lipshutz, J. Org. Chem. 2011, 76, 4697–
4702.
[
[
[
2]
3]
4]
[23] The stereochemical composition of tocopherol methyl ether (15) was
analyzed by means of HPLC using a Daicel Chiracel-OD column and n-
hexane as solvent. While all (2R) diastereomers are base line sepa-
rated all (2S) stereoisomers show up as an unresolved single peak.
[24] For double bond isomerization processes occurring during Ru-
catalyzed olefin metathesis, see, for instance: a) S. H. Hong, M. W.
Day, R. H. Grubbs, J. Am. Chem. Soc. 2004, 126, 7414-7415; b) G.
Vincent, C. Kouklovsky, Chem Eur. J. 2011, 17, 2972-2980; c) B.
Schmidt, S. Hauke, Org. Biomol. Chem. 2013, 11, 4194-4206; d) H.
Guo, R. J. Madhushaw, F.-M. Shen, R.-S. Liu, Tetrahedron 2002, 58,
5627-5637.
a) M. G. Traber, J. Atkinson Free Radic. Biol. Med. 2007, 43, 4-15; b) L.
Packer, S. U. Weber, G. Rimbach, J. Nutr. 2001, 131, 369S-373S; c) E.
Niki, M. G. Traber, Ann. Nutr. Metab. 2012, 61, 207-212.
[
5]
a) D. H. Blatt, W. A. Pryor, J. E. Mata, R. Rodriguez-Proteau, J. Nutr.
Biochem. 2004, 15, 380-395; b) J. K. Lodge, J. Plant Physiol., 2005,
162, 790-796.
[
[
6]
7]
W. Bonrath, T. Netscher, Appl. Catal. A: General 2005, 280, 55-73.
For a review, see: a) T. Netscher, Vitamins and Hormones, 2007, 76,
155-202; for the stereo-controlled set-up of the side chain chirality
centers through asymmetric hydrogenation, see: b) S. Bell, B.
Wüstenberg, S. Kaiser, F. Menges, T. Netscher, A. Pfaltz, Science
[25] Any loss of stereochemical purity of the alkene building block 13 in the
course of its synthesis from 12 could be excluded as described in the
Supporting Information.
2006, 311, 642-644; for more recent catalytic-asymmetric approaches
to control the 2R configuration, see, for instance: c) K. Liu, A. Chougnet,
W.-D. Woggon, Angew. Chem. Int. Ed. 2008, 47, 5827-5829; d) A. O.
Termath, H. Sebode, W. Schlundt, R. T. Stemmler, T. Netscher, W.
Bonrath, H.-G. Schmalz, Chem. Eur. J. 2014, 20, 12051-12055; e) U.
Uria, C. Vila, M.-Y. Lin, M. Rueping, Chem. Eur. J. 2014, 20, 13913-
[26] a) P. N. Rylander, Hydrogenation Methods, London, 1985; b) one
example for Pd/C mediated double bond migration: G. A. Schiehser, J.
D. White, J. Org. Chem. 1980, 45, 1864-1868.
[27] For the hydrogenation conditions used, see a) R. Gabioud, P. Vogel,
Helv. Chim. Acta 1986, 69, 865-872; for a related isomerization-free
hydrogenation in the tocopherol series, see C. Rein, P. Demel, R. A.
Outten, T. Netscher, B. Breit, Angew. Chem. Int. Ed. 2007, 46, 8670-
8673.
13917; f) Z. Wu, S. R. Harutyunyan, A. J. Minnaard, Chem. Eur. J.
2014, 20, 14250-14255; g) P. S. Kaib and B. List, Synlett, 2016, 27,
156-159; h) B. Bieszczad, D. G. Gilheany, Org. Biomol. Chem. 2017,
15, 6483–6492.
[
[
8]
9]
A. O. Termath, J. Velder, R. T. Stemmler, T. Netscher, W. Bonrath, H.-
G. Schmalz, Eur. J. Org. Chem. 2014, 3337–3340.
[28] F. Ratsch, H.-G. Schmalz, Synlett 2018, 29, 785-792.
[29] L. W. K. Moodie, D. S. Larsen, Eur. J. Org. Chem. 2014, 1684-1694.
[30] Y. Gan, D. H. Blank, J. E. Ney, T. A. Spencer, J. Org. Chem. 2006, 71,
5864-5869.
a) T. Seiser, N. Cramer, J. Am. Chem. Soc. 2010, 132, 5340-5341; b)
N. Cramer, T. Seiser, Synlett 2011, 4, 449-460; c) L. Souillart, N.
Cramer, Chem. Rev. 2015, 115, 9410−9464.
[31] J. Cho, Y. M. Lee, D. Kim, S. Kim, J. Org. Chem. 2009, 74, 3900-3904.
[32] H. Takaya, T. Ohta, N. Sayo, H. Kumobayashi, S. Akutagawa, S.-i.
Inoue, I. Kasahara, R. Noyori, J. Am. Chem. Soc. 1987, 109, 1596-
1597.
[
[
10] H. Monenschein, D. B. Horne, M. D. Bartberger, S. A. Hitchcock, T. T.
Nguyen, V. F. Patel, L. D. Pennington, W. Zhong, Bioorg. Med. Chem.
Lett. 2012, 22, 3607-3611.
11] a) M. Hatano, O. Ito, S. Suzuki, K. Ishihara, J. Org. Chem. 2010, 75,
[33] a) S. Kaiser, S. P. Smidt, A. Pfaltz, Angew. Chem. Int. Ed. 2006, 45,
5194-5197; b) A. Wang, B. Wüstenberg, A. Pfaltz, Angew. Chem. Int.
Ed. 2008, 47, 2298-2300.
5008–5016; b) R. Li-Yuan Bao, R. Zhao, L. Shi, Chem. Commun. 2015,
51, 6884-6900.
[
[
[
[
12] T. Imamoto, N. Takiyama, K. Nakamura, T. Hatajima, Y. Kamiya, J. Am.
[34] The diasteromeric ratio could be determined in this case by means of
1H NMR spectroscopy at the stage of ketone 23. Hydrogenation of 21
using the enantiomeric Pfaltz catalyst (derived from ent-L5) mainly
afforded the 4’S-epimer of 22 (d.r. ≥ 95:5).[22] The two diastereomers
showed differences in the NMR only at the stage of 23 (see the
supporting information).
Chem Soc. 1989, 111, 4392-4398.
13] Z. Wu, A. V. R. Madduri, S. R. Harutyunyan, A. J. Minnaard, Eur. J. Org.
Chem. 2014, 2014, 575-582.
14] A. Krasovskiy, F. Kopp, P. Knochel, Angew. Chem. Int. Ed. 2006, 45,
497-500.
15] CCDC 1589361 (3a), 1589362 (4), 1589359 (cis-9), 1589360 (trans-9),
and 1888519 (16) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from the
[35] R. Barner, J. Hübscher, J. Daly, P. Schönholzer, Helv. Chim. Acta
1981, 64, 915-938.
[36] a) C Yuan, B. Liu, Org. Chem. Front. 2018, 5, 106–131; b) P. Chen, Y.
Wu, S. Zhu, H Jiang, Z. Ma, Org. Chem. Front. 2018, 5, 132–150.
Data
Center
via
[
[
16] A control experiment proved the configurational stability of a non-
racemic sample of ent-2 under the reaction conditions of the Rh-
catalyzed cyclobutanol fragmentation according to Scheme 3.
17] For selected examples of Ir-catalyzed C-C-activation, see: a) R. H.
Crabtree, R. P. Dion, D. J. Gibboni, D. V. McGrath, E. M. Holt, J. Am.
Chem. Soc. 1986, 108, 7222-7227; b) T. Nishimura, T. Yoshinaka, Y.
Nishiguchi, Y. Maeda, S. Uemura, Org. Lett. 2005, 12, 2425-2427; c) S.
Tashiro, M. Yamada, M. Shionoya, Angew. Chem. Int. Ed. 2015, 54,
5351–5354; d) J. Yu , H. Yan, C. Zhu, Angew. Chem. Int. Ed. 2016, 55,
1143-1146; c) M. Murai, A. Nishiyama, N. Nishinaka, H. Morita, K.
Takai, Chem. Commun. 2017, 53, 9281-9284.
[18] The absolute configuration of ent-2a was assigned after conversion of
2a into 15 and comparison with an authentic sample using HPLC on a
chiral column.
This article is protected by copyright. All rights reserved.