Phosphoric Acid Catalyzed Desymmetrization of Bicyclic Bislactones Bearing an All-Carbon Stereogenic Center: Total Syntheses of (−)-Rhazinilam and (−)-Leucomidine B†
Jean-Baptiste Gualtierotti
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Search for more papers by this authorDelphine Pasche
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Search for more papers by this authorDr. Qian Wang
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Search for more papers by this authorCorresponding Author
Prof. Dr. Jieping Zhu
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.chSearch for more papers by this authorJean-Baptiste Gualtierotti
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Search for more papers by this authorDelphine Pasche
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Search for more papers by this authorDr. Qian Wang
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Search for more papers by this authorCorresponding Author
Prof. Dr. Jieping Zhu
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.ch
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304. 1015 Lausanne (Switzerland) http://lspn.epfl.chSearch for more papers by this authorWe thank EPFL (Switzerland), the Swiss National Science Foundation (SNSF), the Swiss National Centres of Competence in Research NCCR-Chemical Biology, the COST action (CM0905), and the Swiss State Secretariat for Education and Research for financial support.
Graphical Abstract
Breaking symmetry: Achiral bislactones (1) undergo desymmetrization by reaction with alcohol in the presence of chiral imidodiphosphoric acids. The monoacids 2, having an all-carbon stereogenic center, were obtained in good to excellent yields and enantioselectivities. Concise total syntheses of (−)-rhazinilam and (−)-leucomidine B were subsequently developed using 2 as a common starting material.
Abstract
In the presence of a catalytic amount of an imidodiphosphoric acid, enantioselective desymmetrization of bicyclic bislactones by reaction with alcohols took place smoothly to afford enantiomerically enriched monoacids having an all-carbon stereogenic center. Concise catalytic enantioselective syntheses of both (−)-rhazinilam and (−)-leucomidine B were subsequently developed using (S)-methyl 4-ethyl-4-formylpimelate monoacid as a common starting material.
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References
- 1M. E. Kuehne, J. Am. Chem. Soc. 1964, 86, 2946.
- 2L. Castedo, J. Harley-Mason, M. Kaplan, J. Chem. Soc. D 1969, 1444.
- 3
- 3aJ.-Y. Laronze, J. Laronze-Fontaine, J. Lévy, J. Le Men, Tetrahedron Lett. 1974, 15, 491;
10.1016/S0040-4039(01)82252-8 Google Scholar
- 3bA. Nemes, C. Szántay, Jr., L. Czibula, I. Greiner, ARKIVOC 2008, 154.
- 4Aspidosperma family, see:
- 4aG. Costello, J. E. Saxton, Tetrahedron 1986, 42, 6047;
- 4bJ. W. Blowers, J. E. Saxton, A. G. Swanson, Tetrahedron 1986, 42, 6071; Attempted synthesis of rhazinilam, see:
- 4cC. Carité, J. P. Alazard, K. Ogino, C. Thal, Tetrahedron Lett. 1990, 31, 7011;
- 4dJ.-P. Alazard, C. Terrier, A. Mary, C. Thal, Tetrahedron 1994, 50, 6287.
- 5
- 5aM. Amat, M. Cantó, N. Llor, V. Ponzo, M. Pérez, J. Bosch, Angew. Chem. 2002, 114, 345;
10.1002/1521-3757(20020118)114:2<345::AID-ANGE345>3.0.CO;2-I Google ScholarAngew. Chem. Int. Ed. 2002, 41, 335;10.1002/1521-3773(20020118)41:2<335::AID-ANIE335>3.0.CO;2-Y CAS PubMed Web of Science® Google Scholar
- 5bM. Amat, O. Bassas, N. Llor, M. Cantó, M. Pérez, E. Molins, J. Bosch, Chem. Eur. J. 2006, 12, 7872.
- 6J. C. F. Alves, A. B. C. Simas, P. R. R. Costa, J. D′Angelo, Tetrahedron: Asymmetry 1997, 8, 1963.
- 7
- 7aT. Gerfaud, C. Xie, L. Neuville, J. Zhu, Angew. Chem. 2011, 123, 4040;
10.1002/ange.201100257 Google ScholarAngew. Chem. Int. Ed. 2011, 50, 3954;
- 7bT. Buyck, Q. Wang, J. Zhu, Org. Lett. 2012, 14, 1338;
- 7cT. Buyck, Q. Wang, J. Zhu, Angew. Chem. 2013, 125, 12946;
10.1002/ange.201306663 Google ScholarAngew. Chem. Int. Ed. 2013, 52, 12714;
- 7dZ. Xu, Q. Wang, J. Zhu, Angew. Chem. 2013, 125, 3354; Angew. Chem. Int. Ed. 2013, 52, 3272;
- 7eZ. Xu, Q. Wang, J. Zhu, J. Am. Chem. Soc. 2013, 135, 19127;
- 7fW. Ren, Q. Wang, J. Zhu, Angew. Chem. 2014, 126, 1849; Angew. Chem. Int. Ed. 2014, 53, 1818.
- 8
- 8aT. Akiyama, J. Itoh, K. Yokota, K. Fuchibe, Angew. Chem. 2004, 116, 1592;
10.1002/ange.200353240 Google ScholarAngew. Chem. Int. Ed. 2004, 43, 1566;
- 8bD. Uraguchi, K. Sorimatchi, M. Terada, J. Am. Chem. Soc. 2004, 126, 11804.
- 9
- 9aT. Akiyama, Chem. Rev. 2007, 107, 5744;
- 9bM. Terada, Chem. Commun. 2008, 4097;
- 9cD. Kampen, C. M. Reisinger, B. List, Top. Curr. Chem. 2010, 291, 395;
- 9dM. Terada, Curr. Org. Chem. 2011, 15, 2227;
- 9eM. Rueping, A. Kuenkel, I. Atodiresei, Chem. Soc. Rev. 2011, 40, 4539;
- 9fC. Zheng, S.-L. You, Chem. Soc. Rev. 2012, 41, 2498.
- 10E. García-Urdiales, I. Alfonso, V. Gotor, Chem. Rev. 2005, 105, 313.
- 11
- 11aY. Chen, P. McDavid, L. Deng, Chem. Rev. 2003, 103, 2965;
- 11bL. Atodiresei, I. Schiffers, C. Bolm, Chem. Rev. 2007, 107, 5683.
- 12Chiral phosphoric acid-catalyzed desymmetrization, see:
- 12aS. Xu, Z. Wang, X. Zhang, X. Zhang, K. Ding, Angew. Chem. 2008, 120, 2882; Angew. Chem. Int. Ed. 2008, 47, 2840;
- 12bE. B. Rowland, G. B. Rowland, E. Rivera-Otero, J. C. Antilla, J. Am. Chem. Soc. 2007, 129, 12084;
- 12cK. Mori, T. Katoh, T. Suzuki, T. Noji, M. Yamanaka, T. Akiyama, Angew. Chem. 2009, 121, 9832; Angew. Chem. Int. Ed. 2009, 48, 9652;
- 12dQ.-W. Zhang, C.-A. Fan, H.-J. Zhang, Y.-Q. Tu, Y.-M. Zhao, P. Gu, Z.-M. Chen, Angew. Chem. 2009, 121, 8724; Angew. Chem. Int. Ed. 2009, 48, 8572;
- 12eG. D. Sala, A. Lattanzi, Org. Lett. 2009, 11, 3330;
- 12fV. N. Wakchaure, B. List, Angew. Chem. 2010, 122, 4230;
10.1002/ange.201000637 Google ScholarAngew. Chem. Int. Ed. 2010, 49, 4136;
- 12gQ. Gu, Z.-Q. Rong, C. Zheng, S.-L. You, J. Am. Chem. Soc. 2010, 132, 4056;
- 12hL. Ren, T. Lei, L.-Z. Gong, Chem. Commun. 2011, 47, 11683;
- 12iS. Müller, M. J. Webber, B. List, J. Am. Chem. Soc. 2011, 133, 18534;
- 12jM. Yang, Y.-M. Zhao, S.-Y. Zhang, Y.-Q. Tu, F.-M. Zhang, Chem. Asian J. 2011, 6, 1344;
- 12kD. M. Rubush, M. A. Morges, B. J. Rose, D. H. Thamm, T. Rovis, J. Am. Chem. Soc. 2012, 134, 13554;
- 12lK. Mori, Y. Ichikawa, M. Kobayashi, Y. Shibata, M. Yamanaka, T. Akiyama, J. Am. Chem. Soc. 2013, 135, 3964;
- 12mZ. Wang, Z. Chen, J. Sun, Angew. Chem. 2013, 125, 6817; Angew. Chem. Int. Ed. 2013, 52, 6685;
- 12nZ. Chen, J. Sun, Angew. Chem. 2013, 125, 13838; Angew. Chem. Int. Ed. 2013, 52, 13593;
- 12oG. Qabaja, J. E. Wilent, A. R. Benavides, G. E. Bullard, K. S. Petersen, Org. Lett. 2013, 15, 1266;
- 12pA. D. Lackner, A. V. Samant, F. D. Toste, J. Am. Chem. Soc. 2013, 135, 14090; metal/phosphoric acid catalyzed desymmetrization:
- 12qZ. Chai, T. J. Rainey, J. Am. Chem. Soc. 2012, 134, 3615;
- 12rB. Guo, G. Schwarzwalder, J. T. Njardarson, Angew. Chem. 2012, 124, 5773; Angew. Chem. Int. Ed. 2012, 51, 5675;
- 12sA. K. Mourad, J. Leutzow, C. Czekelius, Angew. Chem. 2012, 124, 11311;
10.1002/ange.201205416 Google ScholarAngew. Chem. Int. Ed. 2012, 51, 11149.
- 13For other recent examples of chiral phosphoric acid catalyzed kinetic resolution/dynamic kinetic resolution, see:
- 13aF.-L. Sun, X.-J. Zheng, Q. Gu, Q.-L. He, S.-L. You, Eur. J. Org. Chem. 2010, 47;
- 13bM. Rueping, U. Uria, M.-Y. Lin, I. Atodiresei, J. Am. Chem. Soc. 2011, 133, 3732;
- 13cC. Wang, H.-W. Luo, L.-Z. Gong, Synlett 2011, 992;
- 13dG. Lu, V. B. Birman, Org. Lett. 2011, 13, 356;
- 13eM. Yamanaka, M. Hoshino, T. Katoh, K. Mori, T. Akiyama, Eur. J. Org. Chem. 2012, 4508;
- 13fX.-S. Wu, S.-K. Tian, Chem. Commun. 2012, 48, 898;
- 13gI. Čorić, J. H. Kim, T. Vlaar, M. Patil, W. Thiel, B. List, Angew. Chem. 2013, 125, 3574;
10.1002/ange.201209983 Google ScholarAngew. Chem. Int. Ed. 2013, 52, 3490;
- 13hS. Harada, S. Kuwano, Y. Yamaoka, K.-I. Yamada, K. Takasu, Angew. Chem. 2013, 125, 10417;
10.1002/ange.201304281 Google ScholarAngew. Chem. Int. Ed. 2013, 52, 10227;
- 13iK. Saito, Y. Shibata, M. Yamanaka, T. Akiyama, J. Am. Chem. Soc. 2013, 135, 11740; silver phosphate catalyzed:
- 13jY. Wang, K. Zheng, R. Hong, J. Am. Chem. Soc. 2012, 134, 4096.
- 14R. Chong, P. S. Clezy, Aust. J. Chem. 1967, 20, 123.
- 15CCDC 1002333 (12 a) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
- 16The structure of the bislactone 12 a in the solid state did not possess an obvious plane of symmetry. However, we use the term desymmetrization in this paper for the sake of convenience.
- 17
- 17aI. Čorić, B. List, Nature 2012, 483, 315;
- 17bS. Liao, I. Čorić, Q. Wang, B. List, J. Am. Chem. Soc. 2012, 134, 10765;
- 17cJ. H. Kim, I. Čorić, S. Vellalath, B. List, Angew. Chem. 2013, 125, 4570; Angew. Chem. Int. Ed. 2013, 52, 4474.
- 18
- 18aI. Čorić, S. Müller, B. List, J. Am. Chem. Soc. 2010, 132, 17370;
- 18bF. Xu, D. Huang, C. Han, W. Shen, X. Lin, Y. Wang, J. Org. Chem. 2010, 75, 8677.
- 19The quality of the monocrystal was not good enough to create a cif file. However, the so generated structure (see the Supporting Information) allowed us to determine without ambiguity the absolute configuration of 2 a.
- 20Isolation:
- 20aD. J. Abraham, R. D. Rosenstein, R. L. Lyon, H. H. S. Fong, Tetrahedron Lett. 1972, 13, 909;
10.1016/S0040-4039(01)84471-3 Google Scholar
- 20bK. T. De Silva, A. H. Ratcliffe, G. F. Smith, G. N. Smith, Tetrahedron Lett. 1972, 13, 913;
10.1016/S0040-4039(01)84472-5 Google Scholar
- 20cfor a review, see: O. Baudoin, D. Guénard, F. Guéritte, Mini-rev. Org. Chem. 2004, 1, 333.
- 21For total synthesis of (±)-rhazinilam, see:
- 21aA. H. Ratcliffe, G. F. Smith, G. N. Smith, Tetrahedron Lett. 1973, 14, 5179;
10.1016/S0040-4039(01)87657-7 Google Scholar
- 21bJ. A. Johnson, D. Sames, J. Am. Chem. Soc. 2000, 122, 6321;
- 21cP. Magnus, T. Rainey, Tetrahedron 2001, 57, 8647;
- 21dA. L. Bowie, Jr., C. C. Hughes, D. Trauner, Org. Lett. 2005, 7, 5207;
- 21eL. McMurray, E. M. Beck, M. J. Gaunt, Angew. Chem. 2012, 124, 9422;
10.1002/ange.201204151 Google ScholarAngew. Chem. Int. Ed. 2012, 51, 9288;
- 21fX. Sui, R. Zhu, G. Li, X, Ma, Z. Gu, J. Am. Chem. Soc. 2013, 135, 9318; for synthesis of (−)-rhazinilam, see:
- 21gJ. A. Johnson, N. Li, D. Sames, J. Am. Chem. Soc. 2002, 124, 6900;
- 21hZ. Liu, A. S. Wasmuth, S. G. Nelson, J. Am. Chem. Soc. 2006, 128, 10352;
- 21iM. G. Banwell, D. A. S. Beck, A. C. Willis, ARKIVOC 2006, 163;
- 21jZ. Gu, A. Zakarian, Org. Lett. 2010, 12, 4224;
- 21kK. Sugimoto, K. Toyoshima, S. Nonaka, K. Kotaki, H. Ueda, H. Tokuyama, Angew. Chem. 2013, 125, 7309;
10.1002/ange.201303067 Google ScholarAngew. Chem. Int. Ed. 2013, 52, 7168.
- 22M. Motegi, A. E. Nugroho, Y. Hirasawa, T. Arai, A. H. A. Hadi, H. Morita, Tetrahedron Lett. 2012, 53, 1227.
- 23Y.-C. Wu, J. Zhu, J. Org. Chem. 2008, 73, 9522.
- 24K. C. Nicolaou, C. J. N. Mathison, T. Montagnon, Angew. Chem. 2003, 115, 4211;
10.1002/ange.200352076 Google ScholarAngew. Chem. Int. Ed. 2003, 42, 4077.
- 25R. Grigg, P. Myers, A. Somasunderam, V. Sridharan, Tetrahedron 1992, 48, 9735.
- 26K. C. Nicolaou, A. A. Estrada, G. C. Freestone, S. H. Lee, X. Alvarez-Mico, Tetrahedron 2007, 63, 6088.
- 27Purification by semipreparative SFC on a chiral OD-H column afforded enantiopure leucomidine B.
