Remote Central-to-Axial Chirality Conversion: Direct Atroposelective Ester to Biaryl Transformation.

作者: Achim Link , Christof Sparr

DOI: 10.1002/ANIE.201803472

关键词: AtropisomerReagentCombinatorial chemistryChemistryArylChirality (chemistry)StereoselectivityAxial chiralityStereocenterSilanes

摘要: A strategy for the remote central-to-axial chirality conversion by simultaneous planarization of an encoding and a transient stereocenter is presented. Based on diastereoselective double addition chiral 1,5-bifunctional organomagnesium alkoxide reagent to broad range aryl ester substrates, axially biaryls are directly obtained upon in situ reduction. Various structurally distinct atropisomeric biaryl silanes that serve as valuable anion surrogates accessible one step with e.r. values up 98:2.

参考文章(46)
M. Mark midland, Alfonso tramontano, Aleksander kazubski, Richard S. graham, David J.S. tsai, Daniel B. cardin, Asymmetric reductions of propargyl ketones : An effective approach to the synthesis of optically-active compounds Tetrahedron. ,vol. 40, pp. 1371- 1380 ,(1984) , 10.1016/S0040-4020(01)82422-4
Anton A Toutov, Wen-Bo Liu, Kerry N Betz, Brian M Stoltz, Robert H Grubbs, Catalytic C-H bond silylation of aromatic heterocycles Nature Protocols. ,vol. 10, pp. 1897- 1903 ,(2015) , 10.1038/NPROT.2015.118
Miroslav Havránek, Dalimil Dvořák, 3,3-Disubstituted allyl alcohols from palladium-catalyzed coupling of hydroaluminated propargyl alcohols with aryl iodides. Journal of Organic Chemistry. ,vol. 67, pp. 2125- 2130 ,(2002) , 10.1021/JO0162235
Ryoji Noyori, Hidemasa Takaya, BINAP: an efficient chiral element for asymmetric catalysis Accounts of Chemical Research. ,vol. 23, pp. 345- 350 ,(1990) , 10.1021/AR00178A005
Fenghai Guo, Leah C. Konkol, Regan J. Thomson, Enantioselective synthesis of biphenols from 1,4-diketones by traceless central-to-axial chirality exchange. Journal of the American Chemical Society. ,vol. 133, pp. 18- 20 ,(2011) , 10.1021/JA108717R
Yoshinori Nishii, Kazunori Wakasugi, Keisuke Koga, Yoo Tanabe, Chirality Exchange from sp3 Central Chirality to Axial Chirality: Benzannulation of Optically Active Diaryl-2,2-dichlorocyclopropylmethanols to Axially Chiral α-Arylnaphthalenes Journal of the American Chemical Society. ,vol. 126, pp. 5358- 5359 ,(2004) , 10.1021/JA0319442
Masatoshi Asami, Teruaki Mukaiyama, Enantioface-differentiating addition of a chiral aryllithium reagent to aldehydes. Chemistry Letters. ,vol. 9, pp. 17- 20 ,(1980) , 10.1246/CL.1980.17