Access to Functionalized E-Allylsilanes and E-Alkenylsilanes through Visible-Light-Driven Radical Hydrosilylation of Mono- and Disubstituted Allenes.

A visible-light-driven radical hydrosilylation of allene has been achieved by using eosin Y as the photocatalyst, with thiol and base as additives. Depending on allenes, two types of adducts with E-selectivity were obtained. It was demonstrated that monosubstituted nonarylated allenes reacted to give linear E-allylsilanes, while 1,3-disubstituted electron-deficient allenes afforded E-alkenylsilanes. A radical mechanism was proposed to account for the chemo-, regio-, and stereoselective formation of these functionalized silicon-containing compounds.

[1]  Z. Yao,et al.  Diastereoselective Synthesis of Polysubstituted Piperidines via Visible Light-Driven Silylative Cyclization of Aza-1,6-Dienes: Experimental and DFT Studies. , 2019, Chemistry.

[2]  Peng‐Fei Xu,et al.  Dehydrogenative Silylation of Alkenes for the Synthesis of Substituted Allylsilanes via Photoredox, HAT, and Cobalt Catalysis. , 2019, Angewandte Chemie.

[3]  Jie Wu,et al.  Visible-Light-Mediated Metal-Free Difunctionalization of Alkenes with CO2 and Silanes or C(sp3 )-H Alkanes. , 2018, Angewandte Chemie.

[4]  Z. Yao,et al.  Visible Light-Driven Radical trans-Hydrosilylation of Electron-Neutral and -Rich Alkenes with Tertiary and Secondary Hydrosilanes. , 2018, The Journal of organic chemistry.

[5]  Maciej Zaranek,et al.  Markovnikov Hydrosilylation of Alkenes: How an Oddity Becomes the Goal , 2018, ACS Catalysis.

[6]  Jie Wu,et al.  Recent Developments in the Photo‐Mediated Generation of Silyl Radicals and Their Application in Organic Synthesis , 2018, ChemPhotoChem.

[7]  Y. Landais,et al.  Thirty Years of (TMS)3SiH: A Milestone in Radical-Based Synthetic Chemistry. , 2018, Chemical reviews.

[8]  Z. Yao,et al.  Radical Hydrosilylation of Alkynes Catalyzed by Eosin Y and Thiol under Visible Light Irradiation. , 2018, Organic letters.

[9]  Xiaoxu Yang,et al.  Dichotomy of Manganese Catalysis via Organometallic or Radical Mechanism: Stereodivergent Hydrosilylation of Alkynes. , 2018, Angewandte Chemie.

[10]  Chao Wang,et al.  Access to stereodefined (Z)-allylsilanes and (Z)-allylic alcohols via cobalt-catalyzed regioselective hydrosilylation of allenes , 2017, Nature Communications.

[11]  Jie Wu,et al.  Visible-Light-Mediated Metal-Free Hydrosilylation of Alkenes through Selective Hydrogen Atom Transfer for Si-H Activation. , 2017, Angewandte Chemie.

[12]  S. Luo,et al.  Iron-Catalyzed Intermolecular 1,2-Difunctionalization of Styrenes and Conjugated Alkenes with Silanes and Nucleophiles. , 2017, Angewandte Chemie.

[13]  Xiaoyong Du,et al.  Advances in Base-Metal-Catalyzed Alkene Hydrosilylation , 2017 .

[14]  David A. Nicewicz,et al.  Organic Photoredox Catalysis. , 2016, Chemical reviews.

[15]  K. Takai,et al.  Synthesis of Linear Allylsilanes via Molybdenum-Catalyzed Regioselective Hydrosilylation of Allenes , 2016 .

[16]  Jian Sun,et al.  Cobalt Complex-Catalyzed Hydrosilylation of Alkenes and Alkynes , 2016 .

[17]  Lizhi Zhang,et al.  A Free-Radical-Promoted Stereospecific Decarboxylative Silylation of α,β-Unsaturated Acids with Silanes. , 2016, Angewandte Chemie.

[18]  D. Dondi,et al.  Decatungstate‐Photocatalyzed Si−H/C−H Activation in Silyl Hydrides: Hydrosilylation of Electron‐Poor Alkenes , 2015 .

[19]  M. Stratakis,et al.  Ligandless Regioselective Hydrosilylation of Allenes Catalyzed by Gold Nanoparticles. , 2015, Organic letters.

[20]  J. Montgomery,et al.  Regiodivergent and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes. , 2015, Angewandte Chemie.

[21]  D. MacMillan,et al.  Alcohols as alkylating agents in heteroarene C–H functionalization , 2015, Nature.

[22]  D. MacMillan,et al.  The direct arylation of allylic sp3 C–H bonds via organocatalysis and photoredox catalysis , 2015, Nature.

[23]  M. Oestreich,et al.  Trans-selective radical silylzincation of ynamides. , 2014, Angewandte Chemie.

[24]  J. Montgomery,et al.  Regioselective allene hydrosilylation catalyzed by N-heterocyclic carbene complexes of nickel and palladium. , 2013, Journal of the American Chemical Society.

[25]  Rong Zeng,et al.  Formal alkylation of allenes through highly selective radical cyclizations of allene-enes. , 2012, Angewandte Chemie.

[26]  G. Pattenden,et al.  Alkene-allenecyclopropane radical cyclisations promoted by tris-(trimethylsilyl)silane , 2009 .

[27]  B. Trost,et al.  Addition of Metalloid Hydrides to Alkynes: Hydrometallation with Boron, Silicon, and Tin , 2005 .

[28]  Y. Landais,et al.  Allylsilanes in Organic Synthesis − Recent Developments , 2004 .

[29]  A. Studer,et al.  Radical transfer hydrosilylation/cyclization using silylated cyclohexadienes. , 2001, Organic letters.

[30]  Yoshinori Yamamoto,et al.  Lewis Acid Catalyzed Highly Regio- and Stereocontrolled Trans-Hydrosilylation of Alkynes and Allenes , 1999 .

[31]  B. P. Roberts.  Polarity-reversal catalysis of hydrogen-atom abstraction reactions: concepts and applications in organic chemistry , 1999 .

[32]  C. Chatgilialoglu.  Structural and Chemical Properties of Silyl Radicals , 1995 .

[33]  B. Giese,et al.  Tris(trimethylsilyl)silane: an efficient hydrosilylating agent of alkenes and alkynes , 1992 .

[34]  C. A. Burkhard,et al.  Alkylation of Hydrochlorosilanes , 1947 .

[35]  F. Whitmore,et al.  PEROXIDE-CATALYZED ADDITION OF TRICHLOROSILANE TO 1-OCTENE , 1947 .