Chemistry - A European Journal
10.1002/chem.201901046
COMMUNICATION
To demonstrate the scalability and utility of the current
protocol, gram-scale synthesis of -allenylic -AAs 3a and 7a
was performed, and comparable yields were obtained with
maintained enantioselectivities. Subsequent acidic hydrolysis
and tosylation furnished 92% yield of 10 with >99% ee and 80%
yield of 11 with 98% ee, respectively (Scheme 3, upside). The
absolute configuration of the 3a and 7a was identified as (S)-
configuration by single-crystal X-ray diffraction analysis of Ts-
protected 10 and 11. Furthermore, with the developed protocol,
catalytic asymmetric synthesis of naturally occurring (S)-2-
aminohexa-4,5-dienoic acid 12 was successfully realized for the
first time. With benzophenone-derived imine ester 6b and
allenylic carbonate 1a as the starting materials, the coupling
product 7b was obtained in 92% yield with 97% ee with the
current dual Cu/Pd catalytic system. Subsequent acidic
hydrolysis of compound 7b directly produced enantiomerically
enriched natural product (S)-12[20,21] (Scheme 3, bottom).
Press: London, 1982; k) H. F. Schuster, G. M. Coppola, Allenes in
Organic Synthesis; Wiley: New York, 1984; l) N. Krause, A. S. K.
Hashmi, Modern Allene Chemistry; VCH: Weinheim, 2004; m) Alcaide,
B.; Almendros, P.; Campo, T. M.; Rodríguez-Acebes, R. Adv. Synth.
Catal. 2007, 349, 749.
[5]
a) A. Hoffmann-Röder, N. Krause, Angew. Chem. Int. Ed. 2004, 43,
1196; Angew. Chem. 2004, 116, 1216; b) R. M. Eglen, R. L. Whiting,
Br. J. Pharmacol. 1989, 98, 1335.
[
[
6]
7]
D. Xu, M. A. Drahl, L. J. Williams, Beilstein J. Org. Chem. 2011, 7, 937.
a) M. Ogasawara, A. Okada, S. Watanabe, L. Fan, K. Uetake, K.
Nakajima, T. Takahashi, Organometallics 2007, 26, 5025; b) S. A.
Benyunes, L. Brandt, A. Fries, M. Green, M. F. Mahon, T. M. T.
Papworth, J. Chem. Soc., Dalton Trans. 1993, 3785.
[
8]
a) Y. Imada, K. Ueno, K. Kutsuwa, S.-I. Murahashi, Chem. Lett. 2002,
140; b) B. M. Trost, D. R. Fandrick, D. C. Dinh, J. Am. Chem. Soc.
2005, 127, 14186; c) Y. Imada, M. Nishida, K. Kutsuwa, S.-I.
Murahashi, T. Naota, Org. Lett. 2005, 7, 5837; d) Y. Imada, M. Nishida,
T. Naota, Tetrahedron Letters 2008, 49, 4915; e) T. Nemoto, M.
Kanematsu, S. Tamura, Y. Hamada, Adv. Synth. Catal. 2009, 351,
In conclusion, we have successfully developed a highly
efficient dual Cu/Pd catalytic system for asymmetric -
allenylation of readily-available aldimine, cyclic and acyclic
ketimine esters. This protocol allows for the rapid construction
of a range of synthetically important nonproteinogenic -
allenylic -amino acids bearing -quaternary or -tertiary
stereogenic center in a highly stereoselective fashion. This
synergistic catalytic system also showcased the potential of
simultaneous control of central and axial chirality with racemic
internal allenylic diethyl phosphate. Furthermore, with the
synergistic Cu/Pd catalytic system, naturally occurring (S)--
allenic -amino acid was synthesized via a catalytic asymmetric
manner for the first time. Further efforts on applications of this
methodology are currently being conducted in our laboratory.
1773; f) B. Wan, S. Ma, Angew. Chem. Int. Ed. 2013, 52, 441; Angew.
Chem. 2013, 125, 459; g) J. Dai, X. Duan, J. Zhou, C. Fu, S. Ma, Chin.
J. Chem. 2018, 36, 387.
[
[
9]
a) Q. Li, C. Fu, S. Ma, Angew. Chem. Int. Ed. 2012, 51, 11783; Angew.
Chem. 2012, 124, 11953; b) Q. Li, C. Fu, S. Ma, Angew. Chem. Int.
Ed. 2014, 53, 6511; Angew. Chem. 2014, 126, 6629.
10] a) J. L. Malleron, J. C. Fiaud, J. Y. Legros, Handbook of Palladium-
Catalyzed Organic Reactions; Academic Press, San Diego, 1997; b) B.
M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395; c) B. M. Trost,
Acc. Chem. Res. 1996, 29, 355; d) J. Tsuji, Palladium Reagents and
Catalysts, Wiley, Chichester, 1995.
[
11] For reviews on Pd-catalyzed Allylic Alkylations, see: a) N. A. Butt, W.
Zhang, Chem. Soc. Rev. 2015, 44, 7929; b) Z. Lu, S. Ma, Angew.
Chem. Int. Ed. 2008, 47, 258; Angew. Chem. 2008, 120, 264; c) J. D.
Weaver, A. Recio, A. J. Grenning, J. A. Tunge, Chem. Rev. 2011, 111,
Acknowledgements
1846; d) J. T. Mohr, B. M. Stoltz, Chem.-Asian J. 2007, 2, 1476.
[
12] For reviews on dual catalysis, see: a) D.-F. Chen, Z.-Y. Han, X.-L.
Zhou, L.-Z. Gong, Acc. Chem. Res. 2014, 47, 2365; b) Z. Du, Z. Shao,
Chem. Soc. Rev. 2013, 42, 1337; c) S. M. Inamdar, V. S. Shinde, N. T.
Patil, Org. Biomol. Chem. 2015, 13, 8116; d) S. Afewerki, A. Cꢀrdova,
Chem. Rev. 2016, 116, 13512; e) A. E. Allen, D. W. C. MacMillan,
Chem. Sci. 2012, 3, 633; f) Z. Shao, H. Zhang, Chem. Soc. Rev. 2009,
This work was supported by NSFC (21525207 and 21772147),
and the Program of Introducing Talents of Discipline to
Universities of China (111 Program) is also appreciated. We
thank Prof. Xudong Qu in School of Pharmacy, Wuhan
University for his generous support.
3
8, 2745.
Keywords: nonproteinogenic -amino acids
synergistic catalysis
asymmetric catalysis
•
allene
•
•
[
13] a) L. Wei, S.-M. Xu, Q. Zhu, C. Che, C.-J. Wang, Angew. Chem. Int.
Ed. 2017, 56, 12312; Angew. Chem. 2017, 129, 12480; b) L. Wei, L.
Xiao, C.-J. Wang, Adv. Synth. Catal. 2018, 360, 3715.
•
asymmetric allenylic alkylation
[
14] a) X. Huo, R. He, J. Fu, J. Zhang, G. Yang, W. Zhang, J. Am. Chem.
Soc. 2017, 139, 9819; b) X. Huo, J. Fu, X. He, J. Chen, F. Xie, W.
Zhang, Chem. Commun. 2018, 54, 599; c) P. Liu, X. Huo, B. Li, R. He,
J. Zhang, T. Wang, F. Xie, W. Zhang, Org. Lett. 2018, 20, 6564; d) K.
Yabushita, A. Yuasa, K. Nagao, A. Ohmiya, J. Am. Chem. Soc. 201 9,
[
1]
a) U. Koert, Nachr. Chem. Technol. Lab. 1995, 43, 347; b) Unnatural
Amino Acids: Methods and Protocols, ed. L. Pollegioni, S. Servi,
Springer, New York, 2012, pp. 1-249; c) D. J. Ager, Amino Acids,
Peptides and Proteins in Organic Chemistry, ed. A. B. Hughes, Wiley-
VCH, Weinheim, 2009, vol. 1, pp. 495-526; d) A. Grauer, B. König, Eur.
J. Org. Chem. 2009, 5099.
141, 113.
[15] For selected reviews, see: a) M. J. O’Donnell, Acc. Chem. Res. 2004,
[
[
2]
3]
a) T. L. Sourkes, Arch. Biochem. Biophys. 1954, 51, 444; b) P. Fasella,
A. Giartosio, G. G. Hammes, Biochemistry 1966, 5, 197; c) D. Schirlin,
F. Gerhart, J. M. Hornsperger, M. Hamon, J. Wagner, M. J. Jung, J.
Med. Chem. 1988, 31, 30.
3
7, 506; b) A. E. Taggi, A. M. Hafez, T. Lectka, Acc. Chem. Res. 2003,
6, 10; c) B. Lygo, B. I. Andrews, Acc. Chem. Res. 2004, 37, 518; d) K.
3
Maruoka, T. Ooi, T. Kano, Chem. Commun. 2007, 1487; e) A. F. M.
Noisier, M. A. Brimble, Chem. Rev. 2014, 114, 8775; f) A. E. Metz, M.
C. Kozlowski, J. Org. Chem. 2015, 80, 1; g) S. Tang, X. Zhang, J. Sun,
D. Niu, J. J. Chruma, Chem. Rev. 2018, 118, 10393.
a) C. Toniolo, H. Brückner, Peptaibiotics: Fungal Peptides Containing
α-Dialkyl α-Amino Acids, Wiley-VCH, Weinheim, 2009; b) B. Bellier, I.
McCort-Tranchenpain, B. Ducos, S. Danascimento, H. Meudal, F.
Noble, C. Garbay, B. P. Roques, J. Med. Chem. 1997, 40, 3947; c) O.
Déry, H. Josien, J. Grassi, G. Chassaing, J. Y. Couraud, S. Lavielle,
Biopolymers 1996, 39, 67.
[
16] a) Z.-Y. Xue, Q.-H. Li, H.-Y. Tao, C.-J. Wang, J. Am. Chem. Soc. 2011,
133, 11757; b) H.-L. Teng, F.-L. Luo, H.-Y. Tao, C.-J. Wang, Org. Lett.
2011, 13, 5600; c) H.-L. Teng, H. Huang, C.-J. Wang, Chem. Eur. J.
2012, 18, 12614; d) Z.-Y. Xue, Z.-M. Song, C.-J. Wang, Org. Biomol.
[
4]
For reviews, see: a) B. Alcaide, P. Almendros, Chem. Soc. Rev. 2014,
Chem. 2015, 13, 5460.
4
3, 2886; b) J. Ye, S. Ma, Acc. Chem. Res. 2014, 47, 989; c) S. Yu, S.
Ma, Angew. Chem. Int. Ed. 2012, 51, 3074; Angew. Chem. 2012, 124,
128; d) S. Ma, Acc. Chem. Res. 2009, 42, 1679; e) S. Ma, Chem.
Rev. 2005, 105, 2829; f) S. Ma, Top. Organomet. Chem. 2005, 14,
83; g) R. W. Bates, V. Satcharoen, Chem. Soc. Rev. 2002, 31, 12; h)
[
17] M. J. O’Donnell, W. D. Bennett, W. A. Bruder, W. N. Jacobsen, K.
Knuth, B. LeClef, R. L. Polt, F. G. Bordwell, S. R. Mrozack, T. A. Cripe,
J. Am. Chem. Soc. 1988, 110, 8520.
3
[18] D. A. Evans, M. J. Dart, J. L. Duffy, D. L. Rieger, J. Am. Chem. Soc.
1
1995, 117, 9073.
D. A. Taylor, Chem. Rev. 1967, 67, 317-359; i) S. Patai, The
Chemistry of Ketenes, Allenes and Related Compounds; Wiley: New
York, 1980; j) S. R. Landor, The Chemistry of the Allenes; Academic
[
19] The reaction with 3,4-allenol-derived secondary allenylic phosphate
rac-13 as the reaction partner was carried out in the presence of the
p
combination of Cu(I)/(S,S )-L3 and Pa(0)/(S or R)-BINAP as dual
This article is protected by copyright. All rights reserved.