10.1002/anie.201806238
Angewandte Chemie International Edition
COMMUNICATION
Keywords: asymmetric catalysis • chiral allenes • chiral furans •
organocatalysis
[1]
[2]
J. H. van’t Hoff, La Chimie dans l’Espace, P. M. Barzendijk (publisher),
Rotterdam, 1875.
a) A. Hoffmann-Röder, N. Krause, Angew. Chem. Int. Ed. 2004, 43,
1196; b) N. Krause, A. S. K. Hashmi, Modern Allene Chemistry, Vol. 1
and 2, Wiley-VCH, Weinheim, 2004.
[3]
a) For reviews: a) R. Zimmer, C. U. Dinesh, E. Nandanan, F. Khan, Chem.
Rev. 2000, 100, 3067; b) R. W. Bates, V. Satcharoen, Chem. Soc. Rev.
2002, 31, 12; c) L. K. Sydnes, Chem. Rev. 2003, 103, 1133. d) S. Ma,
Acc. Chem. Res. 2003, 36, 701; e) S. Ma, Chem. Rev. 2005, 105, 2829;
f) S. Ma, Acc. Chem. Res. 2009, 42, 1679; g) M. Brasholz, H.-U. Reissig,
R. Zimmer, Acc. Chem. Res. 2009, 42, 45; h) F. López, J. L. Mascareñas,
Chem. Eur. J. 2011, 17, 418; i) S. Yu, S. Ma, Angew. Chem. Int. Ed. 2012,
51, 3074; j) T. Lechel, F. Pfrengle, H.-U. Reissig, R. Zimmer, ChemCat-
Chem 2013, 5, 2100; k) J. Ye, S. Ma, Acc. Chem. Res. 2014, 47, 989.
For selected examples using allenes as versatile synthons: l) A. S. K.
Hashmi, Angew. Chem. Int. Ed. 2000, 39, 3590; m) A. S. Dudnik, A. W.
Sromek, M. Rubina, J. T. Kim, A. V. Kel’in, V. Gevorgyan, J. Am. Chem.
Soc. 2008, 130, 1440; n) V. M. Marx, D. J. Burnell, Org. Lett. 2009, 11,
1229; o) H. Wei, H. Zhai, P.-F. Xu, J. Org. Chem. 2009, 74, 2224; p) P.
Rivera-Fuentes, F. Diederich, Angew. Chem. Int. Ed. 2012, 51, 2818.
For recent reviews: a) S. Yu, S. Ma, Chem. Commun., 2011, 47, 5384;
b) J. Ye, S. Ma, Org. Chem. Front. 2014, 1, 1210; c) R. K. Neff, D. E.
Frantz, ACS Catal. 2014, 4, 519; d) W.-D. Chu, Y. Zhang, J. Wang, Catal.
Sci. Technol., 2017, 7, 4570.
[a] Reactions performed with 1 (0.2 mmol) and 2 (0.1 mmol) in toluene (0.4 mL)
at rt for 24 h. The crude reaction mixture was flushed with argon, and Ph3PAuCl
(10 mol%) and AgOTf (10 mol%) were sequentially added. The mixture was
heated to 40 0C for 24 h. The diastereomeric ratio determined by 1H NMR of the
isolated products. Enantiomeric excess determined by UPC2 (see Supporting
Information). [b] The reaction performed with 0.3 mmol of 1 added in two por-
tions (0.2 mmol from the beginning followed by 0.1 mmol 5 h later). BA: Benzoic
acid
[4]
[5]
In an attempt to obtain crystals suitable for X-ray analysis of
chiral allenes 6, a transformation was performed as shown in
Scheme 5. Allene 6b’ was isolated[19] and reacted with 1,3-pro-
panedithiol in the presence of I2 as catalyst, and product 8 was
obtained in 30% yield over two steps in excellent stereoselectivity.
Based on X-ray analysis of 8 combined with experimental/compu-
tational CD,[17] and comparison with previous publications[18] the
absolute configuration of the allenes 6 in Scheme 3 have been
assigned.
For selected examples using enantioenriched propargylic alcohols: a) B.
D. Sherry, F. D. Toste, J. Am. Chem. Soc. 2004, 126, 15978; b) K. M.
Brummond, J. E. DeForrest, Synthesis, 2007, 795; c) X. Pu, J. M. Ready,
J. Am. Chem. Soc. 2008, 130, 10874; d) M. Yang, N. Yokokawa, H. Ohm-
iya, M. Sawamura, Org. Lett. 2012, 14, 816; for selected examples em-
ploying enantioenriched amines: e) V. K.-Y. Lo, M.-K. Wong, C.-M. Che,
Org. Lett. 2008, 10, 517; f) V. K.-Y. Lo, C.-Y. Zhou, M.-K. Wong, C.-M.
Che, Chem. Commun. 2010, 46, 213.
[6]
[7]
[8]
a) J. Deska, J.-E. Bäckvall, Org. Biomol. Chem. 2009, 7, 3379; b) C. M.
Sapu, J.-E. Bäckvall, J. Deska, Angew. Chem. Int. Ed. 2011, 50, 9731;
c) T. Inokuma, M. Furukawa, Y. Suzuki, T. Kimachi, Y. Kobayashi, Y.
Takemoto, ChemCatChem. 2012, 4, 983.
Scheme 5. Formation of a complex tetracyclic compound.
a) J. Yamazaki, T. Watanabe, K. Tanaka, Tetrahedron: Asymmetry, 2001,
12, 669; b) C.-Y. Li, X.-L. Sun, Q. Jing, Y. Tang, Chem. Commun., 2006,
2980; c) C.-Y. Li, B.-H. Zhu, L.-W. Ye, Q. Jing, X.-L. Sun, Y. Tang, Q.
Shen, Tetrahedron, 2007, 63, 8046.
a) W. de Graaf, J. Boersma, G. van Koten, C. J. Elsevier, J. Organomet.
Chem. 1989, 378, 115; b) A. Hoffmann-Röder, N. Krause, Angew. Chem.
Int. Ed. 2002, 41, 2933; c) T. Hayashi, N. Tokunaga, K. Inoue, Org. Lett.
2004, 6, 305; d) M. Ogasawara Tetrahedron: Asymmetry 2009, 20, 259;
e) M. R. Uehling, S. T. Marionni, G. Lalic, Org Lett. 2012, 14, 362; f) Y.
Wang, W. Zhang, S. Ma, J. Am. Chem. Soc. 2013, 135, 11517; g) H. Li,
D. Grassi, L. Guénée, T. Bürgi, A. Alexakis, Chem. Eur. J. 2014, 20,
16694; h) Y. Liu, H. Hu, H. Zheng, Y. Xia, X. Liu, L. Lin, X. Feng, Angew.
Chem. Int. Ed. 2014, 53, 11579; i) W.-D. Chu, L. Zhang, Z. Zhang, Q.
Zhou, F. Mo, Y. Zhang, J. Wang, J. Am. Chem. Soc. 2016, 138, 14558;
j) Y. Liu, X. Liu, H. Hu, J. Guo, Y. Xia, L. Lin, X. Feng, Angew. Chem. Int.
Ed. 2016, 55, 4054; k) K. Zhang, L.-Q. Lu, S. Yao, J.-R. Chen, D.-Q. Shi,
W.-J. Xiao, J. Am. Chem. Soc. 2017, 139, 12847; l) Y. Huang, J. del Pozo,
S. Torker, A. H. Hoveyda, J. Am. Chem. Soc. 2018, 140, 2643; m) H. L.
Sang, S. Yu, S. Ge, Org. Chem. Front. 2018, 5, 1284.
In conclusion, a novel reaction concept affording chiral trisub-
stituted allenes via aminocatalytic activation of aldehydes or ,-
unsaturated aldehydes has been demonstrated. The methodol-
ogy allows for formation of axially chiral trisubstituted allenes in
high yields and excellent stereoselectivities. The utility of this pro-
cedure has been demonstrated via one-pot synthesis of densely
functionalized chiral furan derivatives maintaining the high stere-
oselectivities. In addition, the formation of a complex tetracyclic
compound has been demonstrated.
Acknowledgements
[9]
H. Liu, D. Leow, K.-W. Huang, C.-H. Tang, J. Am. Chem. Soc. 2009, 131,
7212.
This work was made possible by generous support from the Carls-
berg Foundations Semper Aude, FNU, Aarhus University and
DNRS. YL thanks the Chinese Scholarship Foundation for a PhD
fellowship. Thanks are expressed to Professor Daniel Otzen for
assistance with the CD spectra.
[10] T. Hashimoto, K. Sakata, F. Tamakuni, M. J. Dutton, K. Maruoka, Nat.
Chem. 2013, 5, 240.
[11] A. Tap, A. Blond, V. N. Wakchaure, B. List, Angew. Chem. Int, Ed. 2016,
55, 8962.
[12] D. Qian, L. L. Wu, Z. Lin, J. Sun, Nat. Commun. 2017, 8, 567.
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