Organocatalytic asymmetric synthesis of Si-stereogenic silacycles

Brook, M. A. Silicon in Organic, Organometallic, and Polymer Chemistry (Wiley, 2000).Auner, N. & Weis, J. Organosilicon Chemistry lll: From Molecules to Materials (Wiley, 2009).Hiyama, T. & Oestreich, M. Organosilicon Chemistry: Novel Approaches and Reactions (Wiley-VCH, 2019).Franz, A. K. & Wilson, S. O. Organosilicon molecules with medicinal applications. J. Med. Chem. 56, 388–405 (2013).Article 
CAS 
PubMed 

Google Scholar 
Ramesh, R. & Reddy, D. S. Quest for novel chemical entities through incorporation of silicon in drug scaffolds. J. Med. Chem. 61, 3779–3798 (2018).Article 
CAS 
PubMed 

Google Scholar 
Tacke, R. et al. Biological recognition of enantiomeric silanes: syntheses and antimuscarinic properties of optically active (2-aminoethyl)cyclohexyl(hydroxymethyl)phenylsilanes and related quaternary ammonium derivatives. Organometallics 14, 251–262 (1995).Article 
CAS 

Google Scholar 
Igawa, K., Yoshihiro, D., Abe, Y. & Tomooka, K. Enantioselective synthesis of silacyclopentanes. Angew. Chem. Int. Ed. 55, 5814–5818 (2016).Article 
CAS 

Google Scholar 
Xu, L.-W., Li, L., Lai, G.-Q. & Jiang, J.-X. The recent synthesis and application of silicon-stereogenic silanes: a renewed and significant challenge in asymmetric synthesis. Chem. Soc. Rev. 40, 1777–1790 (2011).Article 
CAS 
PubMed 

Google Scholar 
Bauer, J. O. & Strohmann, C. Recent progress in asymmetric synthesis and application of difunctionalized silicon-stereogenic silanes. Eur. J. Inorg. Chem. 2016, 2868–2881 (2016).Oestreich, M. Silicon-stereogenic silanes in asymmetric catalysis. Synlett 2007, 1629–1643 (2007).Rendler, S., Auer, G., Keller, M. & Oestreich, M. Preparation of a privileged silicon-stereogenic silane: Classical versus Kinetic Resolution. Adv. Synth. Catal. 348, 1171–1182 (2006).Article 
CAS 

Google Scholar 
Igawa, K., Takada, J., Shimono, T. & Tomooka, K. Enantioselective synthesis of silanol. J. Am. Chem. Soc. 130, 16132–16133 (2008).Article 
CAS 
PubMed 

Google Scholar 
Igawa, K., Kokan, N. & Tomooka, K. Asymmetric synthesis of chiral silacarboxylic acids and their ester derivatives. Angew. Chem. Int. Ed. 49, 728–731 (2010).Article 
CAS 

Google Scholar 
Bauer, J. O. & Strohmann, C. From an α-functionalized silicon-stereogenic N,O-silane to a monomeric and tetracoordinate tBuLi adduct with lithium-centered chirality. Angew. Chem. Int. Ed. 53, 8167–8171 (2014).Article 
CAS 

Google Scholar 
Bai, X.-F. et al. Lewis-base-mediated diastereoselective silylations of alcohols: synthesis of silicon-stereogenic dialkoxysilanes controlled by chiral aryl BINMOLs. Chem. Asian J. 12, 1730–1734 (2017).Article 
CAS 
PubMed 

Google Scholar 
Corriu, R. J. P. & Moreau, J. J. E. Asymemtric hydrosilylation of ketones catalysed by a chiral rhodium complex. J. Organomet. Chem. 64, 51–54 (1974).Article 

Google Scholar 
Hayashi, T., Yamamoto, K. & Kumada, M. Asymmetric synthesis of bifunctional organosilicon compounds via hydrosilylation. Tetrahedron Lett. 15, 331–334 (1974).Article 

Google Scholar 
Tamao, K., Nakamura, K., Ishii, H., Yamaguchi, S. & Shiro, M. Axially chiral spirosilanes via catalytic asymmetric intramolecular hydrosilylation. J. Am. Chem. Soc. 118, 12469–12470 (1996).Article 
CAS 

Google Scholar 
Igawa, K., Yoshihiro, D., Ichikawa, N., Kokan, N. & Tomooka, K. Catalytic enantioselective synthesis of alkenylhydrosilanes. Angew. Chem. Int. Ed. 51, 12745–12748 (2012).Article 
CAS 

Google Scholar 
Zhan, G. et al. Enantioselective construction of silicon-stereogenic silanes by scandium-catalyzed intermolecular alkene hydrosilylation. Angew. Chem. Int. Ed. 57, 12342–12346 (2018).Article 
ADS 
CAS 

Google Scholar 
Wen, H., Wan, X. & Huang, Z. Asymmetric synthesis of silicon-stereogenic vinylhydrosilanes by cobalt-catalyzed regio- and enantioselective alkyne hydrosilylation with dihydrosilanes. Angew. Chem. Int. Ed. 57, 6319–6323 (2018).Article 
CAS 

Google Scholar 
Lu, W., Zhao, Y. & Meng, F. Cobalt-catalyzed sequential site- and stereoselective hydrosilylation of 1,3- and 1,4-Enynes. J. Am. Chem. Soc. 144, 5233–5240 (2022).Article 
CAS 
PubMed 

Google Scholar 
Wang, L., Lu, W., Zhang, J., Chong, Q. & Meng, F. Cobalt-catalyzed regio-, diastereo- and enantioselective intermolecular hydrosilylation of 1,3-Dienes with prochiral silanes. Angew. Chem. Int. Ed. 61, e202205624 (2022).Article 
ADS 
CAS 

Google Scholar 
Huang, Y.-H. et al. Enantioelective synthesis of silicon-stereogenic mohohydrosilanes by rhodium-catalyzed intramolecular hydrosilylation. Angew. Chem. Int. Ed. 61, e202113052 (2022).Article 
CAS 

Google Scholar 
Zeng, Y. et al. Rhodium-catalyzed dynamic kinetic asymmetric hydrosilylation to access silicon-stereogenic center. Angew. Chem. Int. Ed. 61, e202214147 (2022).Article 
CAS 

Google Scholar 
Corriu, R. J. P. & Moreau, J. E. E. Asymmetric synthesis of alkoxysilanes catalyzed by rhodium complexes. Tetrahedron Lett. 14, 4469–4472 (1973).Article 

Google Scholar 
Schmidt, D. R., O’Malley, S. J. & Leighton, J. L. Catalytic asymmetric silane synthesis: practical access to chiral silanes. J. Am. Chem. Soc. 125, 1190–1191 (2003).Article 
CAS 
PubMed 

Google Scholar 
Zhu, J., Chen, S. & He, C. Catalytic enantioselective dehydrogenative Si–O coupling to access to chiroptical silicon-stereogenic siloxanes and alkoxysilanes. J. Am. Chem. Soc. 143, 5301–5307 (2021).Article 
CAS 
PubMed 

Google Scholar 
Yasutomi, Y., Suematsu, H. & Katsuki, T. Iridium(III)-catalyzed enantioselective Si–H bond insertion and formation of an enantioenriched silicon center. J. Am. Chem. Soc. 132, 4510–4511 (2010).Article 
CAS 
PubMed 

Google Scholar 
Jagannathan, J. R., Fettinger, J. C., Shaw, J. T. & Franz, A. K. Enantioselective Si–H insertion reactions of diarylcarbenes for the synthesis of silicon-stereogenic silanes. J. Am. Chem. Soc. 142, 11674–11679 (2020).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Shintani, R., Moriya, K. & Hayashi, T. Palladium-catalyzed enantioselective desymmetrization of silacyclobutanes: construction of silacylces possessing a tetraorganosilicon stereocenter. J. Am. Chem. Soc. 133, 16440–16443 (2011).Article 
CAS 
PubMed 

Google Scholar 
Zhang, Q.-W. et al. Construction of chiral tetraorganosilicon by tandem desymmetrization of silacyclobutane/intermolecular dehydrogenative silylation. Angew. Chem. Int. Ed. 56, 1125–1129 (2017).Article 
CAS 

Google Scholar 
Chen, H. et al. Rhodium-catalyzed reaction of silacyclobutanes with unactivated alkynes to afford silacyclohexenes. Angew. Chem. Int. Ed. 58, 4695–4699 (2019).Article 
ADS 
CAS 

Google Scholar 
Zhang, J., Yan, N., Ju, C.-W. & Zhao, D. Nickel(0)-catalyzed asymmetric ring expansion toward enanitoenriched silicon-stereogenic benzosiloles. Angew. Chem. Int. Ed. 60, 25723–25728 (2021).Article 
CAS 

Google Scholar 
Wang, X.-C., Li, B., Ju, C.-W. & Zhao, D. Nickel(0)-catalyzed divergent reactions of silacyclobutanes with internal alkynes. Nat. Commun. 13, 3392–3402 (2022).Article 
ADS 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Shintani, R., Otomo, H., Ota, K. & Hayashi, T. Palladium-catalyzed asymmetric synthesis of silicon-stereogenic dibenzosiloles via enanitoselective C–H bond functionalization. J. Am. Chem. Soc. 134, 7305–7308 (2012).Article 
CAS 
PubMed 

Google Scholar 
Yang, B., Yang, W., Guo, Y., You, L. & He, C. Enantioselective silylation of aliphatic C–H bonds for the synthesis of silicon-stereogenic dihydrobenzosiloles. Angew. Chem. Int. Ed. 59, 22217–22222 (2020).Article 
CAS 

Google Scholar 
Mu, D. et al. Streamlined construction of silicon-stereogenic silanes by tandem enantioselective C–H Silylation/Alkene Hydrosilylation. J. Am. Chem. Soc. 142, 13495–13468 (2020).Article 

Google Scholar 
Ma, W., Liu, L.-C., An, K., He, T. & He, W. Rhodium-catalyzed synthesis of chiral monohydrosilanes by intramolecular C–H functionalization of dihydrosilanes. Angew. Chem. Int. Ed. 60, 4245–4251 (2021).Article 
CAS 

Google Scholar 
Guo, Y., Liu, M.-M., Zhu, X., Zhu, L. & He, C. Catalytic asymmetric synthesis of silicon-stereogenic dihydrodibenzosilines: silicon center-to-axial chirality relay. Angew. Chem. Int. Ed. 60, 13887–13891 (2021).Article 
CAS 

Google Scholar 
Zhang, H. & Zhao, D. Synthesis of silicon-stereogenic silanols involving iridium-catalyzed enantioselective C–H silylation of leading to a new ligand scaffold. ACS Catal. 11, 10748–10753 (2021).Article 
CAS 

Google Scholar 
Chen, S. et al. Enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles. Nat. Commun. 12, 1249–1257 (2021).Article 
ADS 
PubMed 
PubMed Central 

Google Scholar 
Chen, S., Zhu, J., Ke, J., Li, Y. & He, C. Enantioselective intermolecular C–H silylation of heteroarenes for the synthesis of acyclic Si-stereogenic silanes. Angew. Chem. Int. Ed. 61, e202117820 (2022).Article 
CAS 

Google Scholar 
Shintani, R., Maciver, E. E., Tamakuni, F. & Hayashi, T. Rhodium-catalyzed asymmetric synthesis of silicon-stereogenic dibenzooxasilines via enantioselective transmetalation. J. Am. Chem. Soc. 134, 16955–16958 (2012).Article 
CAS 
PubMed 

Google Scholar 
Shintani, R., Takagi, C., Ito, T., Naito, M. & Nozaki, K. Rhodium-catalyzed asymmetric synthesis of silicon-stereogenic dibenzosiloles by enantioselective [2+2+2] cycloaddition. Angew. Chem. Int. Ed. 54, 1616–1620 (2015).Article 
CAS 

Google Scholar 
Sato, Y., Takagi, C., Shintani, R. & Nozaki, K. Palladium-catalyzed asymmetric synthesis of silicon-stereogenic 5,10-dihydrophenazasilines via enantioselective 1,5-palladium migration. Angew. Chem. Int. Ed. 56, 9211–9216 (2017).Article 
CAS 

Google Scholar 
Zhang, G. et al. Asymmetric synthesis of silicon-stereogenic silanes by copper-catalyzed desymmetrizing protoboration of vinylsilanes. Angew. Chem. Int. Ed. 59, 11927–11931 (2020).Article 
CAS 

Google Scholar 
Li, S.-S., Sun, S. & Wang, J. Catalytic asymmetric homologation of 4-substituted cyclohexanones with CF3CHN2: enantioselective synthesis of α-trifluoromethyl cycloheptanones. Angew. Chem. Int. Ed. 61, e202115098 (2022).Article 
CAS 

Google Scholar 
Gao, J. et al. Copper-catalyzed desymmetrization of prochiral silanediols to silicon-stereogenic silanols. ACS Catal. 12, 8476–8483 (2022).Article 
CAS 

Google Scholar 
Yuan, W., Zhu, X., Xu, Y. & He, C. Synthesis of Si-stereogenic silanols by catalytic asymmetric hydrolytic oxidation. Angew. Chem. Int. Ed. 61, e202204912 (2022).Article 
ADS 
CAS 

Google Scholar 
Yang, W. et al. Enantioselective hydroxylation of dihydrosilanes to Si-chiral silanols catalyzed by in situ generated copper(II) species. Angew. Chem. Int. Ed. 61, e202205743 (2022).Article 
ADS 
CAS 

Google Scholar 
Xu, L.-W. Desymmetrization catalyzed by transition-metal complexes: enantioselective formation of silicon-stereogenic silanes. Angew. Chem. Int. Ed. 51, 12932–12934 (2012).Article 
CAS 

Google Scholar 
Shintani, R. Recent progress in catalytic enantioselective desymmetrization of prochiral organosilanes for the synthesis of silicon-stereogenic compounds. Synlett 29, 388–396 (2018).Article 
CAS 

Google Scholar 
Wu, Y. & Wang, P. Silicon-stereogenic monohydrosilane: synthesis and applications. Angew. Chem. Int. Ed. 61, e202205382 (2022).Article 
ADS 
CAS 

Google Scholar 
Yuan, W. & He, C. Enantioselective C–H functionalization toward silicon-stereogenic silanes. Synthesis 54, 1939–1950 (2022).Article 
CAS 

Google Scholar 
Huang, W.-S., Wang, Q., Yang, H. & Xu, L.-W. State-of-the-art advances in enantioselective transition-metal-mediated reactions of silacyclobutanes. Synthesis 54, 5400–5408 (2022).Article 
CAS 

Google Scholar 
Djerourou, A.-H. & Blanco, L. Synthesis of optically 2-sila-1,3-propanediols derivatives by enzymatic transesterification. Tetrahedron 32, 6325–6326 (1991).Article 
CAS 

Google Scholar 
Lu, X. et al. Catalytic synthesis of functional silicon-stereogenic silanes through candida antarctica lipase B catalyzed remote desymmetrization of silicon-centered diols. Eur. J. Org. Chem. 2013, 5814–5819 (2013).Liu, H. et al. Stereoselective access to silicon-stereogenic silacycles via the carbene-catalyzed desymmetric benzoin reaction of siladials. ACS Catal. 12, 9864–9871 (2022).Article 
CAS 

Google Scholar 
Zhou, M. et al. Construction of tetrasubstituted silicon-stereogenic silanes via conformational isomerization and N-heterocyclic carbene-catalyzed desymmetrization. ACS Catal. 12, 7781–7788 (2022).Article 
CAS 

Google Scholar 
Zhou, H. et al. Organocatalytic asymmetric synthesis of Si-stereogenic silyl ethers. J. Am. Chem. Soc. 144, 10156–10161 (2022).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Zhou, H. et al. Organocatalytic DYKAT of Si-stereogenic silanes. J. Am. Chem. Soc. 145, 4994–5000 (2023).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Zhang, X.-X., Yang, G., Zhang, Y.-X., Zhou, J. & Yu, J.-S. Highly enantioselective construction of multifunctional silicon-stereogenic silacycles by asymmetric enamine catalysis. Angew. Chem. Int. Ed. 62, e202217724 (2023).Article 
CAS 

Google Scholar 
Kaib, P. S. J., Schreyer, L., Lee, S., Properzi, R. & List, B. Extremely active organocatalysts enable a highly enantioselective addition of allyltrimethylsilane to aldehyde. Angew. Chem. Int. Ed. 55, 13200–13203 (2016).Article 
CAS 

Google Scholar 
Schreyer, L., Properzi, R. & List, B. IDPi catalysis. Angew. Chem. Int. Ed. 58, 12761–12777 (2019).Article 
CAS 

Google Scholar 
Olah, G. A., Husain, A., Gupta, B. G. B., Salem, G. F. & Narang, S. C. Synthetic methods and reactions 104. silylations with in situ generated trimethylsilyltriflate reagent systems. J. Org. Chem. 46, 5212–5214 (1981).Article 
CAS 

Google Scholar 
Morita, T., Okamoto, Y. & Sakurai, H. A simple and efficient preparation of silyl esters and ethers using allyltrimethylsilane/trifluoromethanesulfonic acid. Synthesis 1981, 745–746 (1981).García-García, P., Lay, F., García-García, P., Rabalakos, C. & List, B. A powerful chiral counteranion motif for asymmetric catalysis. Angew. Chem. Int. Ed. 48, 4363–4366 (2009).Article 

Google Scholar 
James, T., van Gemmeren, M. & List, B. Development and applications of disulfonimides in enantioselective organocatalysis. Chem. Rev. 115, 9388–9409 (2015).Article 
CAS 
PubMed 

Google Scholar 
Čorić, I. & List, B. Asymmetric spirocyclization catalyzed by confined Brønsted acids. Nature 483, 315–139 (2012).Article 
ADS 
PubMed 

Google Scholar 
Hoye, T. R., Jeffrey, C. S. & Shao, F. Mosher ester analysis for the determination of absolute configuration of stereogenic (chiral) carbinol carbons. Nat. Protoc. 2, 2451–2458 (2007).Article 
CAS 
PubMed 

Google Scholar 
Allen, D. A., Tomaso, A. E. Jr., Priest, O. P., Hindson, D. F. & Hurlburt, J. L. Mosher amides: determining the absolute stereochemistry of optically-active amines. J. Chem. Educ. 85, 698–700 (2008).Article 
CAS 

Google Scholar 
Liu, L. et al. Confined acid-catalyzed asymmetric carbonyl-ene cyclization. J. Am. Chem. Soc. 137, 13268–13271 (2015).Article 
CAS 
PubMed 

Google Scholar 
Ishihara, K., Nakamura, S. & Yamamoto, H. The first enantioselective biomimetic cyclization of polyprenoids. J. Am. Chem. Soc. 121, 4906–4907 (1999).Article 
CAS 

Google Scholar 
Nakamura, S., Ishihara, K. & Yamamoto, H. Enantioselective biomimetic cyclization of isoprenoids using Lewis acid-assisted chiral Brønsted acids: abnormal Claisen rearrangement and successive cyclizations. J. Am. Chem. Soc. 122, 8131–8140 (2000).Article 
CAS 

Google Scholar 
Ishihara, K., Ishibashi, H. & Yamamoto, H. Enantio- and diastereoselective stepwise cyclization of polyprenoids induced by chiral and achiral LBAs. A new entry to (-)-ambrox, (+)-podocarpa-8,11,13-triene diterpenoids, and (-)-tetracyclic polyprenoid of sedimentary origin. J. Am. Chem. Soc. 124, 3647–3655 (2002).Article 
CAS 
PubMed 

Google Scholar 
Mardirossian, N. & Head-Gordon, M. J. ωB97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation. Chem. Phys. 144, 214110 (2016).ADS 

Google Scholar 
Grimme, S., Hansen, A., Ehlert, S. & Mewes, J.-M. r2SCAN-3c: A “swiss army knife” composite electronic-structure method. J. Chem. Phys. 154, 064103 (2021).Article 
ADS 
CAS 
PubMed 

Google Scholar 
Bursch, M., Mewes, J.-M., Hansen, A. & Grimme, S. Best-practice DFT protocols for basic molecular computational chemistry. Angew. Chem. Int. Ed. 61, e202205735 (2022).Article 
ADS 
CAS 

Google Scholar 
Eames, J. Parallel kinetic resolution. Angew. Chem. Int. Ed. 39, 885–888 (2000).Article 
CAS 

Google Scholar 
Dehli, J. R. & Gotor, V. Parallel kinetic resolution of racemic mixtures: a new strategy for the preparation of enantiopure compounds? Chem. Soc. Rev. 31, 365–370 (2002).Article 
CAS 
PubMed 

Google Scholar 

Hot Topics

Related Articles