Synlett 2022; 33(05): 429-439
DOI: 10.1055/s-0040-1719840
account

Group-Selective Approaches to Complex Natural Product Synthesis: Three Examples of Diastereotopos-Selective Reactions

Ken Ohmori
,
This work was supported by Japan Society for the Promotion of Science (JSPS KAKENHI Grant Numbers JP23000006, JP16H06351, JP16H01137, and JP16H04107).


Dedicated to Profs. Masaji Ohno, Susumu Kobayashi and Reinhard W. Hoffmann

Abstract

This Account showcases three diastereotopos-selective reactions exploited in our complex natural syntheses.

1 Introduction

2 Malyngolide: Hydroalumination of Bisalkynyl tert-Alcohols

3 Cavicularin: Acetal Cleavage

4 Carthamin: Bromoacetoxylation

5 Conclusions



Publication History

Received: 30 August 2021

Accepted after revision: 08 September 2021

Article published online:
13 October 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References

    • 1a Kurihara M, Kamiyama K, Kobayashi S, Ohno M. Tetrahedron Lett. 1985; 26: 5831
    • 1b Ohno M, Kobayashi S, Kurihara M. J. Synth. Org. Chem. Jpn. 1986; 44: 38
    • 1c Hoffman RW. Angew. Chem. Int. Ed. 2003; 42: 1096
    • 2a Greene AE, Luche M.-J, Serra AA. J. Org. Chem. 1985; 50: 3957
    • 2b Harada T, Wada I, Uchimura J, Inoue A, Tanaka S, Oku A. Tetrahedron Lett. 1991; 32: 1219
    • 2c Wipf P, Kim Y. Tetrahedron Lett. 1992; 33: 5477
    • 2d Curran DP, Qi H, DeMello NC, Lin C.-H. J. Am. Chem. Soc. 1994; 116: 8430
    • 2e Curran DP, Geib SJ, Lin C.-H. Tetrahedron: Asymmetry 1994; 5: 199 For selected recent works, see
    • 2f Gollapelli KK, Patil VB, Vinaykumar A, Chegondi R. Chem. Sci. 2021; 12: 1544
    • 2g Kim M, Park B, Shin M, Kim S, Kim J, Baik M.-H, Cho SH. J. Am. Soc. Chem. 2021; 143: 1069
    • 2h Chaheine CM, Gladen PT, Abbasov ME, Romo D. Org. Lett. 2020; 22: 9282
    • 2i Li X, Hall DG. J. Am. Chem. Soc. 2020; 142: 9063
    • 2j Lee J, Chen DY.-K. Angew. Chem. Int. Ed. 2019; 58: 488
    • 2k Inai M, Asakawa T, Kan T. Tetrahedron Lett. 2018; 59: 1343
    • 2l Zeng X.-P, Cao Z.-Y, Wang Y.-H, Zhou F, Zhou J. Chem. Rev. 2016; 116: 7330
    • 2m Borissov A, Davies TQ, Ellis SR, Fleming TA, Richardson MS. W, Dixon DJ. Chem. Soc. Rev. 2016; 45: 5474 For reviews, see
    • 2n Li X, Hall DG. J. Am. Soc. Chem. 2020; 142: 9063
    • 2o Munro KR, Male L, Spencer N, Grainger RS. Org. Biomol. Chem. 2013; 11: 6856
    • 2p Merad J, Candy M, Pons J.-M, Bressy C. Synthesis 2017; 49: 1938
    • 3a Marckwald W. Ber. Dtsch. Chem. Ges. 1904; 37: 1012
    • 3b Erlenmeyer E. Biochem. Z. 1914; 64: 366
    • 4a Hajos ZG, Parrish DR. J. Org. Chem. 1974; 39: 1615
    • 4b Hajos ZG, Parrish DR. Org. Synth. 1985; 63: 25
    • 5a Schreiber SL, Wang Z. J. Am. Chem. Soc. 1985; 107: 5303
    • 5b Schreiber SL, Schreiber TS, Smith DB. J. Am. Soc. Chem. 1987; 109: 1525
    • 5c Poss CS, Schreiber SL. Acc. Chem. Res. 1994; 27: 9
    • 5d Nakatsuka M, Ragan JA, Sammakia T, Smith DB, Uehling DE, Schreiber SL. J. Am. Chem. Soc. 1990; 112: 5583
  • 6 Suzuki T, Ohmori K, Suzuki K. Org. Lett. 2001; 3: 1741
  • 7 Takiguchi H, Ohmori K, Suzuki K. Angew. Chem. Int. Ed. 2013; 52: 10472
    • 8a Hayashi T, Ohmori K, Suzuki K. Synlett 2016; 27: 2345
    • 8b Hayashi T, Ohmori K, Suzuki K. Org. Lett. 2017; 19: 866
    • 8c Azami K, Hayashi T, Kusumi T, Ohmori K, Suzuki K. Angew. Chem. Int. Ed. 2019; 58: 5321
    • 8d Matsuoka S, Azami K, Fujiki Y, Dohi R, Yasuike T, Ohmori K, Suzuki K. Synlett 2021; in press; in press; DOI: DOI: 10.1055/s-0040-1719836.
  • 9 Cardellina JH. II, Moore RE, Arnold EV, Clardy J. J. Org. Chem. 1979; 44: 4039
    • 10a Sakito Y, Tanaka S, Asami M, Mukaiyama T. Chem. Lett. 1980; 1223
    • 10b Srivastava N, Subba ReddyB. V. Helv. Chim. Acta 2016; 99: 267
    • 10c Doran R, Duggan L, Singh S, Duffy CD, Guiry PJ. Eur. J. Org. Chem. 2011; 7097
    • 10d Gutierrez M, Tidgewell K, Capson TL, Engene N, Almanza A, Schemies J, Jung M, Gerwick WH. J. Nat. Prod. 2010; 73: 709
    • 10e Koumbis AE, Dieti KM, Vikentiou MG, Gallos JK. Tetrahedron Lett. 2003; 44: 2513
    • 10f Carda M, Rodriguez S, Castillo E, Bellido A, Diaz-Oltra S, Marco JA. Tetrahedron 2003; 59: 857
    • 10g Mizutani H, Watanabe M, Honda T. Tetrahedron 2002; 58: 8929
    • 10h Wan Z, Nelson SG. J. Am. Chem. Soc. 2000; 122: 10470
    • 10i Trost BM, Tang W, Schulte JL. Org. Lett. 2000; 2: 4013 ; and references therein
  • 11 Nagasawa T, Taya K, Kitamura M, Suzuki K. J. Am. Chem. Soc. 1996; 118: 8949

    • For reviews of hydroalumination, see:
    • 12a Zweifel G, Miller JA. In Organic Reactions, Vol. 32 1984; 375
    • 1212 Eisch, J. J. In Comprehensive Organic Synthesis, Vol. 10.8 Fleming I.; Pergamon Press, Oxford, 1991; 733 For hydroalumination of bisalkynyl alcohols, see:
    • 12c Igawa K, Tomooka K. Angew. Chem. Int. Ed. 2006; 45: 232
    • 12d Tomooka K, Kikuchi M, Igawa K, Suzuki M, Keong P.-H, Nakai T. Angew. Chem. Int. Ed. 2000; 39: 4502
    • 13a Ohmori K, Suzuki T, Taya K, Tanabe D, Ohta T, Suzuki K. Org. Lett. 2001; 3: 1057
    • 13b Ohmori K, Hachisu Y, Suzuki T, Suzuki K. Tetrahedron Lett. 2002; 43: 1031
  • 14 Corey EJ, Kirst H, Katzenellenbogen J. J. Am. Chem. Soc. 1970; 92: 6314
    • 15a Baudine JB, Hareau G, Julia SA, Ruel O. Tetrahedron Lett. 1991; 32: 1175
    • 15b Bellingham R, Jarowicki K, Kocienski P, Martin V. Synthesis 1996; 285
    • 16a Birch AJ. J. Chem. Soc. 1944; 403
    • 16b Evans DA, Kaldor SW, Jones TK, Clardy J, Stout TJ. J. Am. Chem. Soc. 1990; 112: 7001
  • 17 For isolation, see: Toyota M, Yoshida T, Kan Y, Takaoka S, Asakawa Y. Tetrahedron Lett. 1996; 37: 4745
    • 18a Harrowven DC, Woodcock T, Howes PD. Angew. Chem. Int. Ed. 2005; 44: 3899
    • 18b Kostiuk SL, Woodcock T, Dudin LF, Howes PD, Harrowven DC. Chem. Eur. J. 2011; 17: 10906
  • 19 For other synthesis of rac-20, see: Harada K, Makino K, Shima N, Okuyama H, Esumi T, Kubo M, Hioki H, Asakawa Y, Fukuyama Y. Tetrahedron 2013; 69: 6959
  • 20 Takiguchi H, Ohmori K, Suzuki K. Chem. Lett. 2011; 40: 1069
    • 21a Mori K, Ohmori K, Suzuki K. Angew. Chem. Int. Ed. 2009; 48: 5638
    • 21b Mori K, Ohmori K, Suzuki K. Angew. Chem. Int. Ed. 2009; 48: 5633
  • 22 Mislow K, Axelrod M, Rayner DR, Gotthardt H, Coyne LM, Hammond GS. J. Am. Chem. Soc. 1965; 87: 4958
  • 23 Stadlbauer S, Ohmori K, Hattori F, Suzuki K. Chem. Commun. 2012; 48: 8425
  • 24 Tietze LF, Schuffenhauer A, Schreiner PR. J. Am. Chem. Soc. 1998; 120: 7952
    • 25a Calligaris M. Coord. Chem. Rev. 2004; 248: 351
    • 25b Hsu CC, Geanangel RA. Inorg. Chem. 1980; 19: 110
    • 25c Stefano SD, Mazzonna M, Bodo E, Mandolini L, Lanzalunga O. Org. Lett. 2011; 13: 142
  • 26 Geoffroy OJ, Morinelli TA, Meier GP. Tetrahedron Lett. 2001; 42: 5367
  • 27 Bond dissociation energies: 466 kJ/mol for H–C6H5 (cf. 356 kJ/mol for H–CH2C6H5). See: CRC Handbook of Chemistry and Physics, 100th ed.; Boca Raton, 2019; Chapt. 9, 80.
    • 28a Zhao P, Beaudry CM. Org. Lett. 2013; 15: 402
    • 28b Zhao P, Beaudry CM. Angew. Chem. Int. Ed. 2014; 53: 10500
    • 29a Kametaka T, Perkin AG. J. Chem. Soc. Trans. 1910; 97: 1415
    • 29b Kuroda C. J. Chem. Soc. 1930; 752
    • 29c Seshadri TR, Thakur RS. Curr. Sci. 1960; 29: 54
    • 29d Obara H, Onodera J. Chem. Lett. 1979; 8: 201
    • 29e Obara H, Onodera J, Shirasaki F. Chem. Lett. 1980; 9: 1095
    • 29f Takahashi Y, Miyasaka N, Tasaka S, Miura I, Urano S, Ikura M, Hikichi K, Matsumoto T, Wada M. Tetrahedron Lett. 1982; 23: 5163
    • 29g Obara H, Namai S, Machida Y. Chem. Lett. 1986; 15: 495
    • 29h Sato S, Obara H, Kumazawa T, Onodera J, Furuhata K. Chem. Lett. 1996; 25: 833
    • 29i Sato S, Kumazawa T, Watanabe H, Takayanagi K, Matsuba S, Onodera J, Obara H, Furuhata K. Chem. Lett. 2001; 30: 1318
  • 30 For another synthetic route, see: Abe Y, Sohtome T, Sato S. J. Heterocycl. Chem. 2020; 57: 3685
    • 31a Tamura Y, Yakura T, Haruta J, Kita Y. J. Org. Chem. 1987; 52 3927 For contributions from our laboratory, see
    • 31b Yasui Y, Koga Y, Suzuki K, Matsumoto T. Synlett 2004; 615
    • 31c Yasui Y, Suzuki K, Matsumoto T. Synlett 2004; 619
    • 31d Morita M, Ohmori K, Suzuki K. Org. Lett. 2015; 17: 5634, For a review, see
    • 31e Yoshimura A, Zhdankin VV. Chem. Rev. 2016; 116: 3328
    • 32a Moriarty RM, Prakash I, Penmasta R. J. Chem. Soc., Chem. Commun. 1987; 202
    • 32b Moriarty RM, Penmasta R, Awasthi AK, Prakash I. J. Org. Chem. 1988; 53: 6124
    • 33a Urankar D, Rutar I, Modec B, Dolenc D. Eur. J. Org. Chem. 2005; 2349
    • 33b Yamashita Y, Hirano Y, Takada A, Takikawa H, Suzuki K. Angew. Chem. Int. Ed. 2013; 52: 6658