Rhodium-Catalyzed β-Dehydroborylation of Silyl Enol Ethers: Access to Highly Functionalized Enolates.

An efficient rhodium-catalyzed β-dehydroborylation of aldehyde-derived silyl enol ethers (SEEs) with bis(pinacolato)diboron (B2pin2) is disclosed. The borylation reactions proceeded well with alkyl- and aryl-substituted SEEs, affording a wide array of valuable functionalized β-boryl silyl enolates with high efficiency and excellent stereoselectivity. Moreover, the borylated products, through versatile carbon-boron bond transformations, were readily converted into diverse synthetically useful molecules, including α-hydroxy ketones, functionalized SEEs, and gem-difunctionalized aldehydes.

[1]  I. Marek,et al.  Stereodivergent Access to Trisubstituted Alkenylboronate Esters through Alkene Isomerization , 2021, Organic letters.

[2]  Zheng Huang,et al.  Pincer Iron Hydride Complexes for Alkene Isomerization: Catalytic Approach to Trisubstituted (Z)-Alkenyl Boronates , 2021, ACS Catalysis.

[3]  Zhenyang Lin,et al.  Rhodium-Catalyzed Regiodivergent Synthesis of Alkylboronates via Deoxygenative Hydroboration of Aryl Ketones: Mechanism and Origin of Selectivities , 2021, ACS Catalysis.

[4]  Zhenyang Lin,et al.  Enantioselective Rh-Catalyzed Hydroboration of Silyl Enol Ethers. , 2021, Journal of the American Chemical Society.

[5]  I. Marek,et al.  Stereoselective Sc(OTf)3-Catalyzed Aldol Reactions of disubstituted Silyl Enol Ethers of Aldehydes with Acetals. , 2021, Angewandte Chemie.

[6]  Yue Wang,et al.  Direct Synthesis of Multi(boronate) Esters from Alkenes and Alkynes via Hydroboration and Boration Reactions , 2020 .

[7]  Zhenyang Lin,et al.  Rhodium-Catalyzed Deoxygenation and Borylation of Ketones: A Combined Experimental and Theoretical Investigation. , 2020, Journal of the American Chemical Society.

[8]  X. Cui,et al.  Catalyst Development in the Dehydrogenative Borylation of Alkenes for the Synthesis Vinylboronate Esters , 2020, Synlett.

[9]  Yong Ling,et al.  Nickel(II)-Catalyzed Borylation of Alkenyl Methyl Ethers via C-O Bond Cleavage. , 2020, Organic letters.

[10]  P. Stang,et al.  Divergent and Stereoselective Synthesis of Tetraarylethylenes from Vinylboronates. , 2020, Angewandte Chemie.

[11]  Changcheng Jing,et al.  Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles , 2020, Angewandte Chemie.

[12]  Zhange Feng,et al.  Development and Mechanistic Studies of Iron-Catalyzed Construction of Csp2-B Bonds via C-O Bond Activation. , 2020, Organic letters.

[13]  I. Marek,et al.  Stereoselective Access to Fully Substituted Aldehyde Silyl Enol Ethers by Iridium-Catalyzed Alkene Isomerization. , 2020, Angewandte Chemie.

[14]  Wanxiang Zhao,et al.  Oxidation of Alkynyl Boronates to Carboxylic Acids, Esters and Amides. , 2020, Angewandte Chemie.

[15]  Shuanglin Qu,et al.  Rhodium‐Catalyzed Remote C(sp 3 )−H Borylation of Silyl Enol Ethers , 2019, Angewandte Chemie International Edition.

[16]  Guillaume Duret,et al.  Regio- and Stereoselective Synthesis of Fully Substituted Silyl Enol Ethers of Ketones and Aldehydes in Acyclic Systems. , 2019, Angewandte Chemie.

[17]  T. Hosoya,et al.  Synthesis of (2,2-Diborylvinyl)arenes by Rhodium-Catalyzed Desulfanylative gem-Diborylation of 2-Arylvinyl Sulfides. , 2019, Organic letters.

[18]  Wanxiang Zhao,et al.  Stereoselective Synthesis of Vinylboronates by Rh‐Catalyzed Borylation of Stereoisomeric Mixtures , 2019, Chinese Journal of Chemistry.

[19]  N. Mizuno,et al.  Selective Dehydrogenative Mono- or Diborylation of Styrenes by Supported Copper Catalysts , 2019, ACS Catalysis.

[20]  P. Pérez,et al.  Alkenyl Boronates: Synthesis and Applications. , 2019, Chemistry, an Asian journal.

[21]  William B. Reid,et al.  Synthesis of Trisubstituted Alkenyl Boronic Esters from Alkenes Using the Boryl-Heck Reaction. , 2018, Organic letters.

[22]  Jianwei Sun,et al.  Triflimide (HNTf2) in Organic Synthesis. , 2018, Chemical reviews.

[23]  N. Mankad,et al.  Dehydrogenative Borylation and Silylation of Styrenes Catalyzed by Copper-Carbenes , 2017 .

[24]  Hisashi Yamamoto,et al.  Second Generation of Aldol Reaction. , 2016, Accounts of chemical research.

[25]  J. Takaya,et al.  PSiP-Pincer Type Palladium-Catalyzed Dehydrogenative Borylation of Alkenes and 1,3-Dienes , 2013 .

[26]  D. Hall.  Boronic acids : preparation and applications in organic synthesis, medicine and materials , 2011 .

[27]  A. Yudin,et al.  Amphoteric α-boryl aldehydes. , 2011, Journal of the American Chemical Society.

[28]  Javier Magano,et al.  Large-scale applications of transition metal-catalyzed couplings for the synthesis of pharmaceuticals. , 2011, Chemical reviews.

[29]  Pedro M. P. Gois,et al.  Boronic acids and esters in the Petasis-borono Mannich multicomponent reaction. , 2010, Chemical reviews.

[30]  J. Hartwig,et al.  C-H activation for the construction of C-B bonds. , 2010, Chemical reviews.

[31]  N. Miyaura,et al.  Iridium-catalyzed Vinylic C-H Borylation of Cyclic Vinyl Ethers by Bis(pinacolato)diboron , 2008 .

[32]  M. Groll,et al.  20S proteasome and its inhibitors: crystallographic knowledge for drug development. , 2007, Chemical reviews.

[33]  K. Oshima,et al.  Main Group Metals in Organic Synthesis: YAMAMOTO/METALS ORG. 2VLS O-BK , 2005 .

[34]  R. Mahrwald.  Modern aldol reactions , 2004 .

[35]  P. Renaud,et al.  Organoboranes as a source of radicals. , 2001, Chemical reviews.

[36]  J. Otera,et al.  Modern carbonyl chemistry , 2000 .

[37]  Norio Miyaura,et al.  Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds , 1995 .