Catalytic Enantioselective Synthesis of Silicon-Stereogenic Alkoxy­silanes and Siloxanes

Jiefeng Zhu; Chuan He

doi:10.1055/a-1503-7976

Synlett, Table of Contents

Synlett 2021; 32(16): 1575-1580
DOI: 10.1055/a-1503-7976

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Catalytic Enantioselective Synthesis of Silicon-Stereogenic Alkoxysilanes and Siloxanes

Jiefeng Zhu

^aShenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, P. R. of China

^bSchool of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150080, P. R. of China

,

Chuan He ∗

^aShenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, P. R. of China

› Author Affiliations

Abstract

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Abstract

A Rh-catalyzed enantioselective intermolecular dehydrogenative Si–O coupling of dihydrosilanes with alcohols and silanols is demonstrated. Rh(I) catalyst equipped with a Josiphos ligand enables the highly enantioselective alcoholysis process of dihydrosilanes, giving access to a variety of functionalized triorgano-substituted silicon-stereogenic alkoxysilanes and siloxanes in decent yields and ee, which significantly expand the chemical space of the silicon-centered chiral molecules. Utility of this methodology is illustrated by the construction of circularly polarized luminescence (CPL) active chiral alkoxysilane small organic molecules.

1 Introduction

2 Conditions Optimization

3 Substrate Scope

4 Application

5 Conclusions

6 Experimental Procedure

Key words

asymmetric catalysis - dehydrogenative Si−O coupling - silicon-stereogenic alkoxysilanes - silicon-stereogenic siloxanes - CPL-active silanes

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References

References

1a Silicon in Organic, Organometallic and Polymer Chemistry. Brook M. Wiley; New York: 2000
1b The Chemistry of Organic Silicon Compounds. Rappoport Z, Apeloig Y. Wiley; Chichester: 2003
1c Organosilicon Chemistry: Novel Approaches and Reactions. Hiyama T, Oestreich M. Wiley-VCH; Weinheim: 2019

2a Lalonde M, Chan TH. Synthesis 1985; 817
2b Chan TH, Wang D. Chem. Rev. 1992; 92: 995
2c Kamino BA, Bender TP. Chem. Soc. Rev. 2013; 42: 5119
2d Kuroda K, Shimojima A, Kawahara K, Wakabayashi R, Tamura Y, Asakura Y, Kitahara M. Chem. Mater. 2014; 26: 211
2e Xu L.-W, Chen Y, Lu Y. Angew. Chem. Int. Ed. 2015; 54: 9456
2f Issa AA, Luyt AS. Polymers 2019; 11: 537
2g Reyes-Rodriguez GJ, Rezayee NM, Vidal-Albalat A, Jørgensen KA. Chem. Rev. 2019; 119: 4221

3 Weickgenannt A, Oestreich M. In Asymmetric Synthesis: More Methods and Applications. Christmann M, Bräse S. Wiley-VCH; Weinheim: 2012: 35-42

4a Rendler S, Oestreich M. Synthesis 2005; 1727
4b Berry RS. J. Chem. Phys. 1960; 32: 933
4c Couzijn EP. A, Slootweg JC, Ehlers AW, Lammertsma K. J. Am. Chem. Soc. 2010; 132: 18127
4d Moberg C. Angew. Chem. Int. Ed. 2011; 50: 10290

5a Xu L.-W, Li L, Lai G.-Q, Jiang J.-X. Chem. Soc. Rev. 2011; 40: 1777
5b Oestreich M. Synlett 2007; 1629
5c Weickgenannt A, Mewald M, Oestreich M. Org. Biomol. Chem. 2010; 8: 1497
5d Sommer LH, Frye CL. J. Am. Chem. Soc. 1959; 81: 1013
5e Rendler S, Auer G, Keller M, Oestreich M. Adv. Synth. Catal. 2006; 348: 1171
5f Klare HF. T, Oestreich M. Angew. Chem. Int. Ed. 2007; 46: 9335

6a Corriu RJ. P, Moreau JJ. E. Tetrahedron Lett. 1973; 4469
6b Corriu RJ. P, Moreau JJ. E. J. Organomet. Chem. 1976; 120: 337
6c Schmidt DR, O’Malley SJ, Leighton JL. J. Am. Chem. Soc. 2003; 125: 1190

7a Bauer JO, Strohmann C. Eur. J. Inorg. Chem. 2016; 2868
7b Klebe JF, Finkbeiner HL. J. Am. Chem. Soc. 1966; 88: 4740
7c Kobayashi K, Kato T, Unno M, Masuda S. Bull. Chem. Soc. Jpn. 1997; 70: 1393
7d Oestreich M, Schmid UK, Auer G, Keller M. Synthesis 2003; 2725
7e Igawa K, Takada J, Shimono T, Tomooka K. J. Am. Chem. Soc. 2008; 130: 16132
7f Bauer JO, Strohmann C. Angew. Chem. Int. Ed. 2014; 53: 720
7g Bai X.-F, Zou J.-F, Chen M.-Y, Xu Z, Li L, Cui Y.-M, Zheng Z.-J, Xu L.-W. Chem. Asian J. 2017; 12: 1730

8a Xu L.-W. Angew. Chem. Int. Ed. 2012; 51: 12932
8b Shintani R. Asian J. Org. Chem. 2015; 4: 510
8c Shintani R. Synlett 2018; 29: 388

9a Xu J.-X, Chen M.-Y, Zheng Z.-J, Cao J, Xu Z, Cui Y.-M, Xu L.-W. ChemCatChem 2017; 9: 3111
9b Long P.-W, Bai X.-F, Ye F, Li L, Xu Z, Yang K.-F, Cui Y.-M, Zheng Z.-J, Xu L.-W. Adv. Synth. Catal. 2018; 360: 2825

10 Corriu RJ. P, Moreau JJ. E. J. Organomet. Chem. 1974; 64: C51
11 Hayashi T, Yamamoto K, Kumada M. Tetrahedron Lett. 1974; 331
12 Ohta T, Ito M, Tsuneto A, Takaya H. J. Chem. Soc., Chem. Commun. 1994; 2525
13 Shintani R, Maciver EE, Tamakuni F, Hayashi T. J. Am. Chem. Soc. 2012; 134: 16955
14 Kumar R, Hoshimoto Y, Yabuki H, Ohashi M, Ogoshi S. J. Am. Chem. Soc. 2015; 137: 11838

15a Mu D, Yuan W, Chen S, Wang N, Yang B, You L, Zu B, Yu P, He C. J. Am. Chem. Soc. 2020; 142: 13459
15b Yang B, Yang W, Guo Y, You L, He C. Angew. Chem. Int. Ed. 2020; 59: 22217
15c Yuan W, You L, Lin W, Ke J, Li Y, He C. Org. Lett. 2021; 23: 1367
15d Chen S, Mu D, Mai P-L, Ke J, Li Y, He C. Nat. Commun. 2021; 12: 1249
15e Guo Y, Liu M.-M, Zhu X, Zhu L, He C. Angew. Chem. Int. Ed. 2021; in press

16 Zhu J, Chen S, He C. J. Am. Chem. Soc. 2021; 143: 5301

17a Kawakami Y, Kakihana Y, Ooi O, Oishi M, Suzuki K, Shinke S, Uenishi K. Polym. Int. 2009; 58: 279
17b Xue L, Kawakami Y. Polym. J. 2007; 39: 379
17c Wang X.-Q, Zhai X.-Y, Wu B, Bai Y.-Q, Zhou Y.-G. ACS Macro Lett. 2020; 9: 969

18a Riehl JP, Richardson FS. Chem. Rev. 1986; 86 1
18b Kumar J, Nakashima T, Kawai T. J. Phys. Chem. Lett. 2015; 6: 3445
18c Han J, Guo S, Lu H, Liu S, Zhao Q, Huang W. Adv. Opt. Mater. 2018; 6: 1800538
18d Sang Y, Han J, Zhao T, Duan P, Liu M. Adv. Mater. 2020; 32: 1900110

19 Sanchez-Carnerero EM, Agarrabeitia AR, Moreno F, Maroto BL, Muller G, Ortiz MJ, de la Moya S. Chem. Eur. J. 2015; 21: 13488

Catalytic Enantioselective Synthesis of Silicon-Stereogenic Alkoxy­silanes and Siloxanes

Catalytic Enantioselective Synthesis of Silicon-Stereogenic Alkoxysilanes and Siloxanes