Iridium-Catalyzed Asymmetric Umpolung Allylation of N-Fluor­enyl Imines to Prepare 1,4-Disubstituted Homoallylic Amines

Liqiang Wan; Lan Tian; Jie Liu; Dawen Niu

doi:10.1055/s-0036-1588514

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(16): 2051-2056
DOI: 10.1055/s-0036-1588514

synpacts

Iridium-Catalyzed Asymmetric Umpolung Allylation of N-Fluorenyl Imines to Prepare 1,4-Disubstituted Homoallylic Amines

Liqiang Wan

Department of Emergency, West China Hospital, Sichuan University, Chengdu 610041, P. R. of China eMail: niudawen@scu.edu.cn

,

Lan Tian

Department of Emergency, West China Hospital, Sichuan University, Chengdu 610041, P. R. of China eMail: niudawen@scu.edu.cn

,

Jie Liu

Department of Emergency, West China Hospital, Sichuan University, Chengdu 610041, P. R. of China eMail: niudawen@scu.edu.cn

,

Dawen Niu*

Department of Emergency, West China Hospital, Sichuan University, Chengdu 610041, P. R. of China eMail: niudawen@scu.edu.cn

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

The discovery and development of an Ir-catalyzed asymmetric umpolung allylation of imines is discussed here. This method produces 1,4-disubstituted homoallylic amines, a class of compounds that are difficult to access by conventional methods. This reaction proceeds through a sequence involving an allylation and a 2-aza-Cope rearrangement event. The unique mechanistic feature of this reaction could be the reason for its broad substrate scope. The products of this reaction are useful intermediates for various bioactive and natural products. Besides its immediate synthetic utility, we expect this transformation to inspire the development of other umpolung functionalizations of imines and Ir-catalyzed asymmetric allylic substitution (AAS) reactions.

1 Introduction

2 Reaction Discovery

3 Substrate Scope

4 Conclusion

Key words

iridium - allylation - umpolung - imine - enantioselectivity

Volltext

Referenzen

References

For excellent reviews in this topic, see:

1a Helmchen G. Dahnz A. Dübon P. Schelwies M. Weihofen R. Chem. Commun. 2007; 675
1b Helmchen G. In Iridium Complexes in Organic Synthesis . Oro LA. Claver C. Wiley-VCH; Weinheim, Germany: 2009: 211
1c Hartwig JF. Stanley LM. Acc. Chem. Res. 2010; 43: 1461
1d Hartwig JF. Pouy MJ. Top. Organomet. Chem. 2011; 34: 169
1e Liu W.-B. Xia J.-B. You S.-L. Top. Organomet. Chem. 2012; 38: 155
1f Tosatti P. Nelson A. Marsden SP. Org. Biomol. Chem. 2012; 10: 3147

For recent examples, see:

1g Zhan M. Li R.-Z. Mou Z.-D. Cao C.-G. Liu J. Chen Y.-W. Niu D. ACS Catal. 2016; 6: 3381
1h Huang L. Dai L.-X. You S.-L. J. Am. Chem. Soc. 2016; 138: 5793
1i Ye K.-Y. Cheng Q. Zhuo C.-X. You S.-L. Angew. Chem. Int. Ed. 2016; 55: 8113
1j Jiang X. Chen W. Hartwig JF. Angew. Chem. Int. Ed. 2016; 55: 5819
1k Liu W.-B. Reeves CM. Virgil SC. Stoltz BM. J. Am. Chem. Soc. 2013; 135: 10626
1l Liu W.-B. Reeves CM. Stoltz BM. J. Am. Chem. Soc. 2013; 135: 17298

2 Takeuchi R. Kashio M. Angew. Chem. Int. Ed. Engl. 1997; 36: 263
3 Janssen JP. Helmchen G. Tetrahedron Lett. 1997; 38: 8025

4a Chen G. Deng Y. Gong L.-Z. Mi A.-Q. Cui X. Jiang Y.-Z. Choi MC. K. Chan AS. C. Tetrahedron: Asymmetry 2001; 12: 1567
4b Tao Z.-L. Zhang W.-Q. Chen D.-F. Adele A. Gong L.-Z. J. Am. Chem. Soc. 2013; 135: 9255
4c Nakoji M. Kanayama T. Okino T. Takemoto Y. Org. Lett. 2001; 3: 3329
4d Mukherjee S. List B. J. Am. Chem. Soc. 2007; 129: 11336
4e Jiang G.-X. List B. Angew. Chem. Int. Ed. 2011; 50: 9471

For other example, see:

4f Chen D.-F. Han Z.-Y. Zhou X.-L. Gong L.-Z. Acc. Chem. Res. 2014; 47: 2365
4g Yang Z.-P. Zhang W. You S.-L. J. Org. Chem. 2014; 79: 7785 ; and references therein

5a Krautwald S. Sarlah D. Schafroth MA. Carreira EM. Science 2013; 340: 1065
5b Krautwald S. Carreira EM. J. Am. Chem. Soc. 2017; 139: 5627

6a Liu W.-B. He H. Dai L.-X. You S.-L. Org. Lett. 2008; 10: 1815
6b Wu Q.-F. Zheng C. You S.-L. Angew. Chem. Int. Ed. 2012; 51: 1680
6c Zhuo C.-X. Liu W.-B. Wu Q.-F. You S.-L. Chem. Sci. 2012; 3: 205
6d Wu Q.-F. Liu W.-B. Zhuo C.-X. Rong Z.-Q. Ye K.-Y. You S.-L. Angew. Chem. Int. Ed. 2011; 50: 4455
6e Cheng Q. Wang Y. You S.-L. Angew. Chem. Int. Ed. 2016; 55: 3496
6f Yang Z.-P. Wu Q.-F. You S.-L. Angew. Chem. Int. Ed. 2014; 53: 6986
6g Yang Z.-P. Wu Q.-F. Shao W. You S.-L. J. Am. Chem. Soc. 2015; 137: 15899

For excellent reviews in CADA chemistry, see:

7a Zheng C. You S.-L. Chem 2016; 1: 830
7b Zhuo C.-X. Zhang W. You S.-L. Angew. Chem. Int. Ed. 2012; 51: 12662
7c Zhuo C.-X. Zheng C. You S.-L. Acc. Chem. Res. 2014; 47: 2558
7d Wu W.-T. Zhang L. You S.-L. Chem. Soc. Rev. 2016; 45: 1570
7e Liang X.-W. Zheng C. You S.-L. Chem. Eur. J. 2016; 22: 11918

for selected examples of CADA chemistry that are not initiated by Ircatalyzed AAS reaction, see

7f Zheng C. Zhuo C.-X. You S.-L. J. Am. Chem. Soc. 2014; 136: 16251
7g Xu R.-Q. Gu Q. Wu W.-T. Zhao Z.-A. You S.-L. J. Am. Chem. Soc. 2014; 136: 15469
7h Wang S.-G. Yin Q. Zhuo C.-X. You S.-L. Angew. Chem. Int. Ed. 2015; 54: 647
7i Liu C. Yi J.-C. Zheng Z.-B. Tang Y. Dai L.-X. You S.-L. Angew. Chem. Int. Ed. 2016; 55: 751

8a Liang X. Jiang S.-Z. Wei K. Yang Y.-R. J. Am. Chem. Soc. 2016; 138: 2560
8b Jiang S.-Z. Zeng X.-Y. Liang X. Lei T. Wei K. Yang Y.-R. Angew. Chem. Int. Ed. 2016; 55: 4044

9 Kiener CA. Shu C. Incarvito C. Hartwig JF. J. Am. Chem. Soc. 2003; 125: 14272

10a Liu W.-B. He H. Dai L.-X. You S.-L. Synthesis 2009; 2076
10b Liu W.-B. Zheng C. Zhuo C.-X. Dai L.-X. You S.-L. J. Am. Chem. Soc. 2012; 134: 4812

11a Defieber C. Ariger MA. Moriel P. Carreira EM. Angew. Chem. Int. Ed. 2007; 46: 3139
11b Roggen M. Carreira EM. J. Am. Chem. Soc. 2010; 132: 11917

12 Rössler SL. Krautwald S. Carreira EM. J. Am. Chem. Soc. 2017; 139: 3603
13 Liu J. Cao C.-G. Sun H.-B. Zhang X. Niu D. J. Am. Chem. Soc. 2016; 138: 13103
14 Seebach D. Angew. Chem. Int. Ed. Engl. 1979; 18: 239

15a Burger EC. Tunge JA. J. Am. Chem. Soc. 2006; 128: 10002
15b Yeagley AA. Chruma JJ. Org. Lett. 2007; 9: 2879
15c Fields WH. Chruma JJ. Org. Lett. 2010; 12: 316
15d Li Z. Jiang Y.-Y. Yeagley AA. Bour JP. Liu L. Chruma JJ. Fu Y. Chem. Eur. J. 2012; 18: 14527
15e Qian X. Ji P. He C. Zirimwabagabo J. Archibald MM. Yeagley AA. Chruma JJ. Org. Lett. 2014; 16: 5228
15f Tang S. Park JY. Yeagley AA. Sabat M. Chruma JJ. Org. Lett. 2015; 17: 2042
15g Niwa T. Yorimitsu H. Oshima K. Org. Lett. 2008; 10: 4689
15h Niwa T. Suehiro T. Yorimitsu H. Oshima K. Tetrahedron 2009; 65: 5125
15i Chen Y.-J. Kazutuka S. Yamashita Y. Kobayashi S. J. Am. Chem. Soc. 2010; 132: 3244
15j Matsumoto M. Harada M. Yamashita Y. Kobayashi S. Chem. Commun. 2014; 13041
15k Li M. Yücel B. Adrio J. Bellomo A. Walsh PJ. Chem. Sci. 2014; 5: 2383
15l Li M. Berritt S. Walsh PJ. Org. Lett. 2014; 16: 4312
15m Li M. González-Esguevillas M. Berritt S. Yang X. Bellomo A. Walsh PJ. Angew. Chem. Int. Ed. 2016; 55: 2825
15n Liu X. Gao A. Ding L. Xu J. Zhao B. Org. Lett. 2014; 16: 2118
15o Fernández-Salas JA. Marelli E. Nolan SP. Chem. Sci. 2015; 6: 4973

16a Wu Y. Hu L. Li Z. Deng L. Nature 2015; 523: 445
16b Zhu Y. Buchwald SL. J. Am. Chem. Soc. 2014; 136: 4500
16c Chen P. Yue Z. Zhang J. Lv X. Wang L. Zhang J. Angew. Chem. Int. Ed. 2016; 55: 13316
16d For a related reaction, see: Li X. Su J. Liu Z. Zhu Y. Dong Z. Qiu S. Wang J. Lin L. Shen Z. Yan W. Wang K. Wang R. Org. Lett. 2016; 18: 956

17a Tu H.-F. Zheng C. Xu R.-Q. Liu X.-J. You S.-L. Angew. Chem. Int. Ed. 2017; 56: 3237
17b Shen D. Chen Q. Yan P. Zeng X. Zhong G. Angew. Chem. Int. Ed. 2017; 56: 3242

18a Horowitz RM. Geissman TA. J. Am. Chem. Soc. 1950; 72: 1518
18b Sugiura M. Mori C. Kobayashi S. J. Am. Chem. Soc. 2006; 128: 11038
18c Rueping M. Antonchick AP. Angew. Chem. Int. Ed. 2008; 47: 10090
18d Ren H. Wulff WD. J. Am. Chem. Soc. 2011; 133: 5656
18e Ren H. Wulff WD. Org. Lett. 2013; 15: 242
18f Goodman CG. Johnson JS. J. Am. Chem. Soc. 2015; 137: 14574

19 Jones AD. Knight DW. Hibbs DE. J. Chem. Soc., Perkin Trans. 1 2001; 1182

Iridium-Catalyzed Asymmetric Umpolung Allylation of N-Fluor­enyl Imines to Prepare 1,4-Disubstituted Homoallylic Amines

Iridium-Catalyzed Asymmetric Umpolung Allylation of N-Fluorenyl Imines to Prepare 1,4-Disubstituted Homoallylic Amines