CC BY-ND-NC 4.0 · Synthesis 2019; 51(01): 1-30
DOI: 10.1055/s-0037-1610386
review
Copyright with the author

Palladium-Catalyzed Asymmetric Allylic Alkylation Strategies for the Synthesis of Acyclic Tetrasubstituted Stereocenters

Barry M. Trost  *
Department of Chemistry, Stanford University, 335 Campus Drive, Stanford, CA 94305, USA   eMail: bmtrost@stanford.edu   eMail: schultz2@stanford.edu
,
Johnathan E. Schultz 
› InstitutsangabenFunding was provided in part by the Tamaki Foundation.
Weitere Informationen

Publikationsverlauf

Received: 23. Oktober 2018

Accepted: 24. Oktober 2018

Publikationsdatum:
05. Dezember 2018 (online)

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Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

Over the past 20 years, the asymmetric synthesis of acyclic tetrasubstituted stereocenters by Pd-catalyzed asymmetric allylic alkylation (Pd-AAA) strategies has seen considerable growth. Despite the inherent difficulty in accessing acyclic tetrasubstituted stereocenters, creative approaches toward this problem have resulted in high stereoinduction on both electrophilic and nucleophilic reaction partners. Much of this chemistry has paved the way for unique solutions in Mo-, Ir-, and Rh-AAA, with many complimentary methods arising due to the unique regiochemical outcomes of AAA outside of Pd catalysis.

1 Introduction

2 Stereocontrol on Prochiral Electrophiles

3 Stereocontrol on Prochiral Nucleophiles

4 Temporary Cyclic Pronucleophiles

5 Allylic Alkylation with Other Metals

6 Conclusions and Outlook

Key words

allylic alkylation - acyclic stereocontrol - tertiary alcohols - α-tertiary amines - quaternary carbon stereocenters
 

  • References

    • 1a Trost BM, Van Vranken DL. Chem. Rev. 1996; 96: 395
      CrossrefPubMed
    • 1b Trost BM, Crawley ML. Chem. Rev. 2003; 103: 2921
      CrossrefPubMed
    • 1c Trost BM. J. Org. Chem. 2004; 69: 5813
      CrossrefPubMed
    • 1d Trost BM, Machacek MR, Aponick A. Acc. Chem. Res. 2006; 39: 747
      CrossrefPubMed
    • 1e Trost BM, Fandrick DR. Aldrichimica Acta 2007; 40: 59
  • 2 Although the term quaternary stereocenter is sometimes used interchangeably with tetrasubstituted stereocenter, for the sake of this review, quaternary stereocenters will only be applied to all-carbon quaternary stereocenters
  • 3 Trost BM, Jiang C. J. Am. Chem. Soc. 2001; 123: 12907
    CrossrefPubMed
  • 4 Trost BM, McEachern EJ, Toste FD. J. Am. Chem. Soc. 1998; 120: 12702
    Crossref
  • 5 Trost BM, McEachern EJ. J. Am. Chem. Soc. 1999; 121: 8649
    Crossref
  • 6 Trost BM, Jiang C, Hammer K. Synthesis 2005; 3335
    Artikel in Thieme Connect
  • 7 Trost BM, Bunt RC, Lemoine R, Calkins TL. J. Am. Chem. Soc. 2000; 122: 5968
    Crossref
  • 8 Trost BM, Calkins TL, Oertelt C, Zambrano J. Tetrahedron Lett. 1998; 39: 1713
    Crossref
  • 9 The π-allyl complex that places the higher priority group cis to the central hydrogen is denoted as the syn isomer
  • 10 Trost BM, Toste FD. J. Am. Chem. Soc. 1999; 121: 4545
    Crossref
  • 11 Feng J, Holmes M, Krische MJ. Chem. Rev. 2017; For a review on metal-catalyzed synthesis of acyclic quaternary stereocenters: 117: 12564
    CrossrefPubMed
  • 12 For a review on diversity-oriented synthesis: Galloway WR. J. D, Isidro-Llobet A, Spring DR. Nat. Commun. 2010; 1: 80; DOI: 10.1038/ncomms1081
  • 13 Du D, Li L, Xie Z. Angew. Chem. Int. Ed. 2009; 48: 7853
    CrossrefPubMed
  • 14 Trost BM, Dong G, Vance JA. Chem.–Eur. J. 2010; 16: 6265
    PubMed
  • 15 Fagnou K, Lautens M. Angew. Chem. Int. Ed. 2002; 41: 26
    CrossrefPubMed
  • 16 Trost BM, Andersen NG. J. Am. Chem. Soc. 2002; 124: 14320
    CrossrefPubMed
  • 17 Trost BM, Tang W, Schulte JL. Org. Lett. 2000; 2: 4013
    CrossrefPubMed
  • 18 Mandal AK, Schneekloth JS, Crews CM. Org. Lett. 2005; 7: 3645
    CrossrefPubMed
  • 19 Zeng M, Murphy SK, Herzon SB. J. Am. Chem. Soc. 2017; 139: 16377
    CrossrefPubMed
  • 20 Trost BM, Malhotra S, Chan WH. J. Am. Chem. Soc. 2011; 133: 7328
    CrossrefPubMed
  • 21 Zhang P, Le H, Kyne RE, Morken JP. J. Am. Chem. Soc. 2011; 133: 9716
    CrossrefPubMed
  • 22 Ardolino MJ, Morken JP. Tetrahedron 2015; 71: 6409
    CrossrefPubMed
  • 23 Hou X.-L, Sun N. Org. Lett. 2004; 6: 4399
    CrossrefPubMed
    • 24a Trost BM, Toste FD. J. Am. Chem. Soc. 1999; 121: 3543
      Crossref
    • 24b Trost BM, Toste FD. J. Am. Chem. Soc. 2003; 125: 3090
      CrossrefPubMed
  • 25 Sawamura M, Nagata H, Sakamoto H, Ito Y. J. Am. Chem. Soc. 1992; 114: 2586
    Crossref
  • 26 Sawamura M, Nakayama Y, Tang W.-M, Ito Y. J. Org. Chem. 1996; 61: 9090
    Crossref
  • 27 Sawamura M, Sudoh M, Ito Y. J. Am. Chem. Soc. 1996; 118: 3309
    Crossref
  • 28 Mizuho Y, Kasuga N, Komiya S. Chem. Lett. 1991; 2127
  • 29 Sawamura M, Hamashima H, Ito Y. J. Am. Chem. Soc. 1992; 114: 8295
    Crossref
  • 30 Kuwano R, Ito Y. J. Am. Chem. Soc. 1999; 121: 3236
    Crossref
  • 31 Kuwano R, Nishio R, Ito Y. Org. Lett. 1999; 1: 837
    Crossref
  • 32 Kuwano R, Uchida K, Ito Y. Org. Lett. 2003; 5: 2177
    CrossrefPubMed
  • 33 Zhang K, Peng Q, Hou X.-L, Wu Y.-D. Angew. Chem. Int. Ed. 2008; 47: 1741
    CrossrefPubMed
  • 34 Jiang G, List B. Angew. Chem. Int. Ed. 2011; 50: 9471
    CrossrefPubMed
  • 35 Ohmatsu K, Ito M, Kurieda T, Ooi T. Nat. Chem. 2012; 4: 473
    CrossrefPubMed
  • 36 Fujita T, Yamamoto T, Morita Y, Chen H, Shimizu Y, Kanai M. J. Am. Chem. Soc. 2018; 140: 5899
    CrossrefPubMed
  • 37 Belanger E, Houze C, Guimond N, Cantin K, Paquin J.-F. Chem. Commun. 2008; 3251
    PubMed
  • 38 Wang W, Shen H, Wan X.-L, Chen Q.-Y, Guo Y. J. Org. Chem. 2014; 79: 6347
    CrossrefPubMed
  • 39 Weaver JD, Recio AIII, Grenning AJ, Tunge JA. Chem. Rev. 2011; 111: 1846
    CrossrefPubMed
  • 40 Keith JA, Behenna DC, Sherden N, Mohr JT, Ma S, Marinescu SC, Nielsen RJ, Oxgaard J, Stoltz BM, Goddard WA. J. Am. Chem. Soc. 2012; 134: 19050
    CrossrefPubMed
  • 41 Trost BM, Xu J, Schmidt T. J. Am. Chem. Soc. 2009; 131: 18343
    CrossrefPubMed
  • 42 Trost BM, Xu J, Reichle M. J. Am. Chem. Soc. 2007; 129: 282
    CrossrefPubMed
  • 43 Ariyarathna J, Tunge JA. Org. Biomol. Chem. 2014; 12: 8386
    CrossrefPubMed
  • 44 Minko Y, Pasco M, Lercher L, Botoshansky M, Marek I. Nature (London) 2012; 490: 522
  • 45 Starkov P, Moore JT, Duquette DC, Stoltz BM, Marek I. J. Am. Chem. Soc. 2017; 139: 9615
    CrossrefPubMed
  • 46 Alexy EJ, Zhang H, Stoltz BM. J. Am. Chem. Soc. 2018; 140: 10109
    CrossrefPubMed
    • 47a Li BX, Le DN, Mack KA, McClory A, Lim N.-K, Cravillion T, Savage S, Han C, Collum DB, Zhang H, Gosselin F. J. Am. Chem. Soc. 2017; 139: 10777
      CrossrefPubMed
    • 47b Mack KA, McClory A, Zhang H, Gosselin F, Collum DB. J. Am. Chem. Soc. 2017; 139: 12182
      CrossrefPubMed
  • 48 Kuwano R, Naoki I, Murakami M. Chem. Commun. 2005; 3951
    PubMed
  • 49 Maki K, Kanai M, Shibasaki M. Tetrahedron 2007; 63: 4250
    Crossref
    • 50a Trost BM, Ariza X. J. Am. Chem. Soc. 1999; 121: 10727
      Crossref
    • 50b Trost BM, Ariza X. Angew. Chem., Int. Ed. Engl. 1997; 36: 2635
      Crossref
    • 51a Trost BM, Czabaniuk LC. J. Am. Chem. Soc. 2012; 134: 5778
      CrossrefPubMed
    • 51b Trost BM, Czabaniuk LC. Chem.–Eur. J. 2013; 19: 15210
      PubMed
  • 52 Trost BM, Lee CB. J. Am. Chem. Soc. 1998; 120: 6818
    Crossref
  • 53 Seto M, Roizen JL, Stoltz BM. Angew. Chem. Int. Ed. 2008; 47: 6873
    CrossrefPubMed
  • 54 Estipona BI, Pritchett BP, Craig RA, Stoltz BM. Tetrahedron 2016; 72: 3707
    CrossrefPubMed
  • 55 Behenna DC, Liu Y, Yurino T, Kim J, White DE, Virgil SC, Stoltz BM. Nat. Chem. 2012; 4: 130
    CrossrefPubMed
  • 56 Numajiri Y, Jiménez-Osés G, Wang B, Houk KN, Stoltz BM. Org. Lett. 2015; 17: 1082
    CrossrefPubMed
  • 57 Alexy EJ, Virgil SC, Bartberger MD, Stoltz BM. Org. Lett. 2017; 19: 5007
    CrossrefPubMed
  • 58 Hartwig JF, Stanley L. Copper-Catalyzed Allylic Substitution . In Organotransition Metal Chemistry: From Bonding to Catalysis . Hartwig JF. University Science Books; Mill Valley: 2010: 999-1008
    Google Scholar
  • 59 Trost BM, Dogra K. J. Am. Chem. Soc. 2002; 124: 7256
    CrossrefPubMed
  • 61 Trost BM, Dogra K, Franzini M. J. Am. Chem. Soc. 2004; 126: 1944
    CrossrefPubMed
  • 62 Trost BM, Miller JR, Hoffman CM. Jr. J. Am. Chem. Soc. 2011; 133: 8165
    CrossrefPubMed
  • 63 Kanayama T, Yoshida D, Miyabe H, Takemoto K. Angew. Chem. Int. Ed. 2003; 42: 2054
    CrossrefPubMed
  • 64 Hethcox JC, Shockley SE, Stoltz BM. ACS Catal. 2016; 6: 6207
    CrossrefPubMed
  • 65 Krautwald S, Sarlah D, Schafroth MA, Carreira EM. Science (Washington, D. C.) 2013; 340: 1065
    CrossrefPubMed
  • 66 Shockley SE, Hethcox JC, Stoltz BM. Angew. Chem. Int. Ed. 2017; 56: 11545
    CrossrefPubMed
  • 67 Evans PA, Oliver S, Chae J. J. Am. Chem. Soc. 2012; 134: 19314
    CrossrefPubMed
  • 68 Evans PA, Oliver S. Org. Lett. 2013; 15: 5626
    CrossrefPubMed
  • 69 Turnbull BW. H, Oliver S, Evans PA. J. Am. Chem. Soc. 2015; 137: 15374
    CrossrefPubMed
  • 70 Turnbull BW. H, Evans PA. J. Am. Chem. Soc. 2015; 137: 6156
    CrossrefPubMed
  • 71 Wright TB, Evans PA. J. Am. Chem. Soc. 2016; 138: 15303
    CrossrefPubMed