Asymmetric Desymmetrization of Substituted Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation and Theoretical Calculations of Its Mechanistic Aspects

Yuki Naganawa; Jun-ichi Ito; Mayu Kawagishi; Hisao Nishiyama

doi:10.1055/s-0036-1590873

Synthesis, Inhaltsverzeichnis

Synthesis 2017; 49(19): 4448-4460
DOI: 10.1055/s-0036-1590873

feature

Asymmetric Desymmetrization of Substituted Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation and Theoretical Calculations of Its Mechanistic Aspects

Yuki Naganawa*

^aInterdisciplinary Research Center for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8565, Japan eMail: yuki.naganawa@aist.go.jp

,

Jun-ichi Ito

^bDepartment of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan eMail: hnishi@apchem.nagoya-u.ac.jp

,

Mayu Kawagishi

^bDepartment of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan eMail: hnishi@apchem.nagoya-u.ac.jp

,

Hisao Nishiyama*

^bDepartment of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan eMail: hnishi@apchem.nagoya-u.ac.jp

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Asymmetric desymmetrization was demonstrated by means of transition-metal-catalyzed conjugate reduction with hydrosilanes as reductants. Chiral rhodium-bis(oxazolinyl)phenyl complexes [Rh(Phebox-R)] were found to be effective catalysts for conjugate hydrosilylation of differently γ,γ-disubstituted cyclohexadienones to provide the corresponding product with chiral quaternary centers. The mechanistic consideration was also performed by theoretical calculation. These attempts provided information about i) the initial activation of Rh(III) complex into Rh(I) species assisted by hydrosilanes, ii) the complete catalytic cycle, and iii) an explanation of the asymmetric induction and the difference of the structure of cyclohexadienones in enantioselectivity.

Key words

asymmetric synthesis - desymmetrization - quaternary center - rhodium - hydrosilane - conjugate reduction - computational study

Volltext

Referenzen

References
1 Willis MC. J. Chem. Soc., Perkin Trans. 1 1999; 1765

2a Zeng X.-P. Cao Z.-Y. Wang Y.-H. Zhou F. Zhou J. Chem. Rev. 2016; 116: 7330
2b Peterson KS. Tetrahedron Lett. 2015; 56: 6523

3a Fuji K. Chem. Rev. 1993; 93: 2037
3b Christoffers J. Mann A. Angew. Chem. Int. Ed. 2001; 40: 4591
3c Cozzi PG. Hilgraf R. Zimmermann N. Eur. J. Org. Chem. 2007; 5969
3d Bella M. Gasperi T. Synthesis 2009; 1583
3e Quasdorf KW. Overman LE. Nature 2014; 516: 181
3f Corey EJ. Guzman-Perez A. Angew. Chem. Int. Ed. 1998; 37: 388
3g Douglas CJ. Overman LE. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 5363
3h Trost BM. Jiang C. Synthesis 2006; 369

4a Hong AY. Stoltz BM. Eur. J. Org. Chem. 2013; 2745
4b Peterson EA. Overman LE. Proc. Natl. Acad. Sci. U. S. A. 2004; 101: 11943
4c Horwitz MA. Johnson JS. Eur. J. Org. Chem. 2017; 1381

5 Imbos R. Brilman MH. G. Pineschi M. Feringa BL. Org. Lett. 1999; 1: 623
6 Hayashi Y. Gotoh H. Tamura T. Yamaguchi H. Masui R. Shoji M. J. Am. Chem. Soc. 2005; 127: 16028
7 Gu Q. You S.-L. Chem. Sci. 2011; 2: 1519
8 Du J.-Y. Zeng C. Han X.-J. Qu H. Zhao X.-H. An X.-T. Fan C.-A. J. Am. Chem. Soc. 2015; 137: 4267
9 Yao L. Liu K. Tao H.-Y. Qiu G.-F. Zhou X. Wang C.-J. Chem. Commun. 2013; 49: 6078
10 Miyamae N. Watanabe N. Moritaka M. Nakano K. Ichikawa Y. Kotsuki H. Org. Biomol. Chem. 2014; 12: 5847
11 Takagi R. Nishi T. Org. Biomol. Chem. 2015; 13: 11039
12 Chauhan P. Mahajan S. Kaya U. Valkonen A. Rissanen K. Enders D. Adv. Synth. Catal. 2016; 358: 3173

13a Ito J.-i. Nishiyama H. Synlett 2012; 23: 509
13b Nishiyama H. Ito J.-i. Chem. Commun. 2010; 46: 203

14a Kanazawa Y. Tsuchiya Y. Kobayashi K. Shiomi T. Ito J.-i. Kikuchi M. Yamamoto Y. Nishiyama H. Chem. Eur. J. 2006; 12: 63
14b Itoh K. Tsuruta A. Ito J.-i. Yamamoto Y. Nishiyama H. J. Org. Chem. 2012; 77: 10914

15 Naganawa Y. Kawagishi M. Ito J.-i. Nishiyama H. Angew. Chem. Int. Ed. 2016; 55: 6873
16 Han Y. Breitler S. Zheng S.-L. Corey EJ. Org. Lett. 2016; 18: 6172
17 Kress S. Johnson T. Weisshar F. Lautens M. ACS Catal. 2016; 6: 747
18 Liu T.-L. Ng TW. Zhao Y. J. Am. Chem. Soc. 2017; 139: 3643
19 Inokoishi Y. Sasakura N. Nakano K. Ichikawa Y. Kotsuki H. Org. Lett. 2010; 12: 1616
20 Smith LK. Baxendale IR. Org. Biomol. Chem. 2015; 13: 9907
21 CCDC-1548477 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
22 Yang Y.-F. Shi T. Zhang X.-H. Tang Z.-X. Wen Z.-Y. Quan J.-M. Wu Y.-D. Org. Biomol. Chem. 2011; 9: 5845
23 For details of optimized structures, see the Supporting Information.
24 Crombie L. Tuchinda P. Powell MJ. J. Chem. Soc., Perkin Trans. 1 1982; 1477
25 Frisch MJ. Trucks GW. Schlegel HB. Scuseria GE. Robb MA. Cheeseman JR. Scalmani G. Barone V. Mennucci B. Petersson GA. Nakatsuji H. Caricato M. Li X. Hratchian HP. Izmaylov AF. Bloino J. Zheng G. Sonnenberg JL. Hada M. Ehara M. Toyota K. Fukuda R. Hasegawa J. Ishida M. Nakajima T. Honda Y. Kitao O. Nakai H. Vreven T. Montgomery JA. Peralta JE. Ogliaro F. Bearpark MJ. Heyd J. Brothers EN. Kudin KN. Staroverov VN. Keith T. Kobayashi R. Normand J. Raghavachari K. Rendell AP. Burant JC. Iyengar SS. Tomasi J. Cossi M. Rega N. Millam JM. Klene M. Knox JE. Cross JB. Bakken V. Adamo C. Jaramillo J. Gomperts R. Stratmann RE. Yazyev O. Austin AJ. Cammi R. Pomelli C. Ochterski JW. Martin RL. Morokuma K. Zakrzewski VG. Voth GA. Salvador P. Dannenberg JJ. Dapprich S. Daniels AD. Farkas Ö. Foresman JB. Ortiz JV. Cioslowski J. Fox DJ. Gaussian 09, Revision D.01 . Gaussian Inc; Wallingford USA: 2013

Zusatzmaterial

Supporting Information