Robust, chiral, and porous BINAP-based metal-organic frameworks for highly enantioselective cyclization reactions

Journal of the American Chemical Society
Takahiro SawanoWenbin Lin

Abstract

We report here the design of BINAP-based metal-organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh(nbd)2BF4 and [Rh(nbd)Cl]2/AgSbF6, the MOF precatalysts I·Rh(BF4) and I·Rh(SbF6) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. I·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee's) and 4-7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, I·Rh is inactive in the more sterically encumbered Pauson-Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, II·Rh, effectively catalyzed Pauson-Khan...Continue Reading

References

Jul 15, 1994·Cell·M Buckingham
Mar 28, 1996·Chemical Reviews·Iwao OjimaRobert J. Donovan
Mar 14, 2002·Chemical Reviews·Corinne AubertMax Malacria
Apr 27, 2002·Organic Letters·Takanori ShibataKentaro Takagi
Jul 18, 2002·Accounts of Chemical Research·Owen R Evans, Wenbin Lin
Sep 18, 2002·Accounts of Chemical Research·Barry M Trost
Oct 12, 2002·The Journal of Organic Chemistry·Takanori ShibataKentaro Takagi
Mar 15, 2003·Science·Tehshik P Yoon, Eric N Jacobsen
Sep 18, 2003·Journal of the American Chemical Society·Aiguo HuWenbin Lin
Jan 23, 2004·Chemical Society Reviews·Jaime Blanco-UrgoitiJavier Pérez-Castells
Apr 1, 2005·Angewandte Chemie·Susan E Gibson, Nello Mainolfi
Apr 20, 2005·Accounts of Chemical Research·Gérard FéreyFranck Millange
Jun 23, 2005·Journal of the American Chemical Society·Chuan-De WuWenbin Lin
Jul 20, 2005·Angewandte Chemie·Jesse L C Rowsell, Omar M Yaghi
Jun 17, 2006·Chemical Communications : Chem Comm·So-Hye ChoThomas E Albrecht-Schmitt
Apr 3, 2008·Angewandte Chemie·Véronique MicheletJean-Pierre Genêt
Jul 19, 2008·Chemical Reviews·Eloísa Jiménez-Núñez, Antonio M Echavarren
Aug 9, 2008·Angewandte Chemie·Mircea Dincă, Jeffrey R Long
Sep 27, 2008·Journal of the American Chemical Society·Jasmina Hafizovic CavkaKarl Petter Lillerud
Apr 23, 2009·Chemical Society Reviews·Liqing MaWenbin Lin
Apr 23, 2009·Chemical Society Reviews·M D AllendorfR J T Houk
Apr 23, 2009·Chemical Society Reviews·JeongYong LeeJoseph T Hupp
Jan 15, 2010·Current Opinion in Chemical Biology·Rachel C HuxfordWenbin Lin
Oct 1, 2010·Journal of the American Chemical Society·Dongbin DangChunying Duan
Jun 9, 2011·Accounts of Chemical Research·Joseph Della RoccaWenbin Lin
Jun 22, 2011·Chemical Reviews·Yuanjing CuiBanglin Chen
Jun 23, 2011·Chemical Communications : Chem Comm·Feijie SongWenbin Lin
Nov 11, 2011·Chemical Reviews·Lauren E KrenoJoseph T Hupp
Nov 17, 2011·Chemical Reviews·Minyoung YoonKimoon Kim
Dec 16, 2011·Chemical Reviews·Patricia HorcajadaChristian Serre
Dec 24, 2011·Chemical Reviews·Myunghyun Paik SuhDae-Woon Lim
Dec 30, 2011·Chemical Reviews·Kenji SumidaJeffrey R Long
Apr 11, 2012·Angewandte Chemie·Frederik VermoorteleDirk E De Vos
May 2, 2012·Journal of the American Chemical Society·Chengfeng ZhuYong Cui
Jun 8, 2012·Chemical Society Reviews·Angela MarinettiArnaud Voituriez

❮ Previous
Next ❯

Citations

Sep 13, 2016·Journal of the American Chemical Society·Xiao Yu, Seth M Cohen
Nov 30, 2016·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Franziska DracheStefan Kaskel
Jun 28, 2016·Angewandte Chemie·Shuai YuanHong-Cai Zhou
Jan 4, 2017·Chemical Communications : Chem Comm·Markus M HerlingJosef Breu
Jun 21, 2016·Chemical Communications : Chem Comm·Xiaoping ZhangSeth M Cohen
Apr 11, 2018·Chemical Communications : Chem Comm·Jun-Sheng QinHong-Cai Zhou
Jul 7, 2018·Chemistry : a European Journal·Ram R R PrasadMatthew L Clarke
Apr 5, 2019·Chemistry : a European Journal·Teppei YamadaNobuo Kimizuka
Jul 10, 2019·Chemical Communications : Chem Comm·Hong JiangYong Cui
Dec 21, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Félicien BeaubrasPaul-Alain Jaffrès
Oct 21, 2016·Advanced Materials·Bin LiBanglin Chen
Nov 18, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaoqing GuoHongwei Hou
Dec 24, 2018·Chemical Communications : Chem Comm·Yingmu ZhangHong-Cai Zhou
Feb 5, 2021·Angewandte Chemie·Rajashree NewarKuntal Manna
May 12, 2021·Chemical Society Reviews·Juan LiuJian Zhang
Oct 13, 2017·Journal of the American Chemical Society·Lauren C BurrowsKay M Brummond
Aug 20, 2021·Journal of the American Chemical Society·R Eric SikmaSimon M Humphrey
Nov 6, 2018·Journal of the American Chemical Society·Chunxia TanYong Cui
May 2, 2020·Chemical Reviews·Yong-Sheng WeiQiang Xu

❮ Previous
Next ❯

Related Concepts

Related Feeds

Antibodies: Agglutination

Antibody-mediated agglutination is the clumping of cells in the presence of antibody, which binds multiple cells together. This enhances the clearance of pathogens. Find the latest research on antibody-mediated agglutination here.