Highly Regioselective Allylic Substitution Reactions Catalyzed by an Air-Stable (π-Allyl)iridium Complex Derived from Dinaphthocyclooctatetraene and a Phosphoramidite Ligand

Ke-Yin Ye; Zhuo-An Zhao; Zeng-Wei Lai; Li-Xin Dai; Shu-Li You

doi:10.1055/s-0033-1339187

Synthesis, Inhaltsverzeichnis

Synthesis 2013; 45(15): 2109-2114
DOI: 10.1055/s-0033-1339187

special topic

Highly Regioselective Allylic Substitution Reactions Catalyzed by an Air-Stable (π-Allyl)iridium Complex Derived from Dinaphthocyclooctatetraene and a Phosphoramidite Ligand

Ke-Yin Ye

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Fax: +86(21)54925087 eMail: slyou@sioc.ac.cn

,

Zhuo-An Zhao

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Fax: +86(21)54925087 eMail: slyou@sioc.ac.cn

,

Zeng-Wei Lai

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Fax: +86(21)54925087 eMail: slyou@sioc.ac.cn

,

Li-Xin Dai

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Fax: +86(21)54925087 eMail: slyou@sioc.ac.cn

,

Shu-Li You*

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Fax: +86(21)54925087 eMail: slyou@sioc.ac.cn

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Abstract

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Abstract

An air-stable (π-allyl)iridium complex derived from dinaphthocyclooctatetraene and a phosphoramidite ligand has been synthesized and found to be highly efficient in iridium-catalyzed allylic substitution reactions. This catalyst features excellent regioselectivity and high stability. When NaCH(CO₂Me)₂ was used as the nucleophile, the catalyst loading in allylic alkylation reactions can be as low as 0.01 mol%.

Key words

(π-allyl)iridium complex - allylic substitution - enantioselectivity - regioselectivity - dinaphthocyclooctatetraene

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Referenzen

References

For reviews:

1a Trost BM. Chem. Rev. 1996; 96: 395
1b Trost BM, Crawley ML. Chem. Rev. 2003; 103: 2921
1c Lu Z, Ma S. Angew. Chem. Int. Ed. 2008; 47: 258
1d Förster S, Helmchen G, Kazmaier U In Catalytic Asymmetric Synthesis . 3rd ed.; Ojima I. Wiley; Hoboken: 2010: 49

For reviews:

2a Miyabe H, Takemoto Y. Synlett 2005; 1641
2b Takeuchi R, Kezuka S. Synthesis 2006; 3349
2c Helmchen G, Dahnz A, Dübon P, Schelwies M, Weihofen R. Chem. Commun. 2007; 675
2d Helmchen G In Iridium Complexes in Organic Synthesis . Oro LA, Claver C. Wiley-VCH; Weinheim: 2009: 211
2e Hartwig JF, Stanley LM. Acc. Chem. Res. 2010; 43: 1461
2f Hartwig JF, Pouy MJ. Top. Organomet. Chem. 2011; 34: 169
2g Liu W.-B, Xia J.-B, You S.-L. Top. Organomet. Chem. 2012; 38: 155
2h Tosatti P, Nelson A, Marsden SP. Org. Biomol. Chem. 2012; 10: 3147

Selected recent examples:

3a Stanley LM, Bai C, Ueda M, Hartwig JF. J. Am. Chem. Soc. 2010; 132: 8918
3b Roggen M, Carreira EM. J. Am. Chem. Soc. 2010; 132: 11917
3c Giacomina F, Riat D, Alexakis A. Org. Lett. 2010; 12: 1156
3d Zheng S, Gao N, Liu W, Liu D, Zhao X, Cohen T. Org. Lett. 2010; 12: 4454
3e Teichert JF, Fañanás-Mastral M, Feringa BL. Angew. Chem. Int. Ed. 2011; 50: 688
3f Gao N, Zheng S, Yang W, Zhao X. Org. Lett. 2011; 13: 1514
3g Chen W, Hartwig JF. J. Am. Chem. Soc. 2012; 134: 15249
3h Lafrance M, Roggen M, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 3470
3i Schafroth MA, Sarlah D, Krautwald S, Carreira EM. J. Am. Chem. Soc. 2012; 134: 20276
3j Cui R, Guo X, Zheng S, Zhao X. Chin. J. Chem. 2012; 30: 2647
3k Hamilton JY, Sarlah D, Carreira EM. J. Am. Chem. Soc. 2013; 135: 994
3l Chen W, Hartwig JF. J. Am. Chem. Soc. 2013; 135: 2068
3m Kim D, Lee JS, Kong SB, Han H. Angew. Chem. Int. Ed. 2013; 52: 4203
3n Kim D, Reddy S, Singh OV, Lee JS, Kong SB, Han H. Org. Lett. 2013; 15: 512
3o Lee JS, Kim D, Lozano L, Kong SB, Han H. Org. Lett. 2013; 15: 554

4a Streiff S, Welter C, Schelwies M, Lipowsky G, Miller N, Helmchen G. Chem. Commun. 2005; 2957
4b Welter C, Dahnz A, Brunner B, Streiff S, Dübon P, Helmchen G. Org. Lett. 2005; 7: 1239
4c Gnamm C, Förster S, Miller N, Brödner K, Helmchen G. Synlett 2007; 790
4d Gnamm C, Franck G, Miller N, Stork T, Brödner K, Helmchen G. Synthesis 2008; 3331

5 Anton DR, Crabtree RH. Organometallics 1983; 2: 621
6 Spiess S, Welter C, Franck G, Taquet J.-P, Helmchen G. Angew. Chem. Int. Ed. 2008; 47: 7652

Selected examples of allylic substitution reactions catalyzed by [Ir(dbcot)Cl]₂:

7a Franck G, Brödner K, Helmchen G. Org. Lett. 2010; 12: 3886
7b Tosatti P, Horn J, Campbell AJ, House D, Nelson A, Marsden SP. Adv. Synth. Catal. 2010; 352: 3153
7c Tosatti P, Campbell AJ, House D, Nelson A, Marsden SP. J. Org. Chem. 2011; 76: 5495
7d Gärtner M, Mader S, Seehafer K, Helmchen G. J. Am. Chem. Soc. 2011; 133: 2072
7e Gärtner M, Jäkel M, Achatz M, Sonnenschein C, Tverskoy O, Helmchen G. Org. Lett. 2011; 13: 2810
7f Ye K.-Y, Dai L.-X, You S.-L. Org. Biomol. Chem. 2012; 10: 5932

8a Ye K.-Y, He H, Liu W.-B, Dai L.-X, Helmchen G, You S.-L. J. Am. Chem. Soc. 2011; 133: 19006
8b Zhuo C.-X, Liu W.-B, Wu Q.-F, You S.-L. Chem. Sci. 2012; 3: 205
8c Wu Q.-F, Zheng C, You S.-L. Angew. Chem. Int. Ed. 2012; 51: 1680
8d Liu W.-B, Zheng C, Zhuo C.-X, Dai L.-X, You S.-L. J. Am. Chem. Soc. 2012; 134: 4812
8e Liu W.-B, Zhang X, Dai L.-X, You S.-L. Angew. Chem. Int. Ed. 2012; 51: 5183
8f Xu Q.-L, Dai L.-X, You S.-L. Chem. Sci. 2013; 4: 97

9 Welter C, Koch O, Lipowsky G, Helmchen G. Chem. Commun. 2004; 896
10 Shu C, Leitner A, Hartwig JF. Angew. Chem. Int. Ed. 2004; 43: 4797
11 Singh OV, Han H. Tetrahedron Lett. 2007; 48: 7094

12a Madrahimov ST, Markovic D, Hartwig JF. J. Am. Chem. Soc. 2009; 131: 7228
12b Spiess S, Raskatov JA, Gnamm C, Brödner K, Helmchen G. Chem. Eur. J. 2009; 15: 11087
12c Raskatov JA, Spiess S, Gnamm C, Brödner K, Rominger F, Helmchen G. Chem. Eur. J. 2010; 16: 6601
12d Madrahimov ST, Hartwig JF. J. Am. Chem. Soc. 2012; 134: 8136
12e Raskatov JA, Jäkel M, Straub BF, Rominger F, Helmchen G. Chem. Eur. J. 2012; 18: 14314

13a Wender PA, Christy JP. J. Am. Chem. Soc. 2007; 129: 13402
13b Wender PA, Christy JP, Lesser AB, Gieseler MT. Angew. Chem. Int. Ed. 2009; 48: 7687
13c Wender PA, Lesser AB, Sirois LE. Angew. Chem. Int. Ed. 2012; 51: 2736

14a Alexakis A, Rosset S, Allamand J, March S, Guillen F, Benhaim C. Synlett 2001; 1375
14b Naasz R, Arnold LA, Minnaard AJ, Feringa BL. Angew. Chem. Int. Ed. 2001; 40: 927
14c Tissot-Croset K, Polet D, Gille S, Hawner C, Alexakis A. Synthesis 2004; 2586

15 Wuts PG. M, Ashford SW, Anderson AM, Atkins JR. Org. Lett. 2003; 5: 1483
16 Ohmura T, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 15164
17 Nemoto T, Sakamoto T, Matsumoto T, Hamada Y. Tetrahedron Lett. 2006; 47: 8737
18 Brown N, Xie B, Markina N, VanderVelde D, Perchellet J.-PH, Perchellet EM, Crow KR, Buszek KR. Bioorg. Med. Chem. Lett. 2008; 18: 4876

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