Facile insertion of a cyclic alkyl(amino) carbene carbon into the B-B bond of diboron(4) reagents.

We report herein the room temperature insertion of the carbene carbon atom of the cyclic (alkyl)(amino) carbene cAACMe into the B-B single bonds of the diboron(4) compounds B2pin2, B2cat2, B2neop2, and B2eg2 (pin = pinacolato, cat = catecholato, neop = neopentylglycolato, eg = ethyleneglycolato).

[1]  U. Radius,et al.  Reactivity of NHC Alane Adducts towards N-Heterocyclic Carbenes and Cyclic (Alkyl)(amino)carbenes: Ring Expansion, Ring Opening, and Al-H Bond Activation. , 2017, Chemistry.

[2]  U. Radius,et al.  Reversible Oxidative Addition at Carbon. , 2017, Angewandte Chemie.

[3]  G. Bertrand,et al.  Cyclic (Alkyl)(amino)carbenes (CAACs): Recent Developments. , 2017, Angewandte Chemie.

[4]  U. Radius,et al.  What Wanzlick Did Not Dare To Dream: Cyclic (Alkyl)(amino)carbenes (cAACs) as New Key Players in Transition‐Metal Chemistry , 2017 .

[5]  A. Friedrich,et al.  B-B bond activation and NHC ring-expansion reactions of diboron(4) compounds, and accurate molecular structures of B2(NMe2)4, B2eg2, B2neop2 and B2pin2. , 2017, Dalton transactions.

[6]  Hajime Ito,et al.  Transition-metal-free B-B and B-interelement reactions with organic molecules. , 2017, Chemical Society reviews.

[7]  U. Radius,et al.  Adduct Formation, B-H Activation and Ring Expansion at Room Temperature from Reactions of HBcat with NHCs. , 2016, Chemistry.

[8]  S. Geier,et al.  Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse. , 2016, Chemical reviews.

[9]  U. Radius,et al.  25 years of N-heterocyclic carbenes: activation of both main-group element-element bonds and NHCs themselves. , 2016, Dalton transactions.

[10]  D. Stalke,et al.  Insertion of Cyclic Alkyl(amino) Carbene into the Si-H Bonds of Hydrochlorosilanes. , 2016, Inorganic chemistry.

[11]  U. Radius,et al.  Room temperature ring expansion of N-heterocyclic carbenes and B-B bond cleavage of diboron(4) compounds. , 2015, Chemistry.

[12]  Rian D. Dewhurst,et al.  sp(2)-sp(3) diboranes: astounding structural variability and mild sources of nucleophilic boron for organic synthesis. , 2015, Chemical communications.

[13]  J. Wang,et al.  Synthesis, Structure, and Reactivity of Anionic sp(2) -sp(3) Diboron Compounds: Readily Accessible Boryl Nucleophiles. , 2015, Chemistry.

[14]  T. B. Marder,et al.  Zinc-catalyzed borylation of primary, secondary and tertiary alkyl halides with alkoxy diboron reagents at room temperature. , 2014, Angewandte Chemie.

[15]  Sha‐Hua Huang,et al.  Formal carbon insertion of N-tosylhydrazone into B-B and B-Si bonds: gem-diborylation and gem-silylborylation of sp3 carbon. , 2014, Organic letters.

[16]  U. Radius,et al.  C-N bond cleavage and ring expansion of N-heterocyclic carbenes using hydrosilanes. , 2012, Angewandte Chemie.

[17]  A. Whiting,et al.  Catalytic methodologies for the β-boration of conjugated electron deficient alkenes. , 2012, Organic & biomolecular chemistry.

[18]  H. Gulyás,et al.  Trivalent boron nucleophile as a new tool in organic synthesis: reactivity and asymmetric induction. , 2012, Chemical Society reviews.

[19]  Li Dang,et al.  DFT Studies on the Mechanisms of the Platinum-Catalyzed Diboration of Acyclic α,β-Unsaturated Carbonyl Compounds , 2012 .

[20]  D. Apperley,et al.  Spectroscopic and structural characterization of the CyNHC adduct of B2pin2 in solution and in the solid state. , 2012, The Journal of organic chemistry.

[21]  A. Hoveyda,et al.  Metal-free catalytic C-Si bond formation in an aqueous medium. Enantioselective NHC-catalyzed silyl conjugate additions to cyclic and acyclic α,β-unsaturated carbonyls. , 2011, Journal of the American Chemical Society.

[22]  W. Santos,et al.  Structure and reactivity of a preactivated sp2-sp3 diboron reagent: catalytic regioselective boration of α,β-unsaturated conjugated compounds. , 2011, The Journal of organic chemistry.

[23]  Jason D. Masuda,et al.  Activation of Si-H, B-H, and P-H bonds at a single nonmetal center. , 2010, Angewandte Chemie.

[24]  G. Bertrand,et al.  Stable cyclic carbenes and related species beyond diaminocarbenes. , 2010, Angewandte Chemie.

[25]  Amadeu Bonet,et al.  Metal-free catalytic boration at the beta-position of alpha,beta-unsaturated compounds: a challenging asymmetric induction. , 2010, Angewandte Chemie.

[26]  Li Dang,et al.  A facile route to aryl boronates: room-temperature, copper-catalyzed borylation of aryl halides with alkoxy diboron reagents. , 2009, Angewandte Chemie.

[27]  A. Hoveyda,et al.  Efficient C-B bond formation promoted by N-heterocyclic carbenes: synthesis of tertiary and quaternary B-substituted carbons through metal-free catalytic boron conjugate additions to cyclic and acyclic alpha,beta-unsaturated carbonyls. , 2009, Journal of the American Chemical Society.

[28]  Amadeu Bonet,et al.  Asymmetric induction on beta-boration of alpha,beta-unsaturated compounds: an inexpensive approach. , 2009, Dalton transactions.

[29]  Li Dang,et al.  DFT Studies on the Borylation of α,β-Unsaturated Carbonyl Compounds Catalyzed by Phosphine Copper(I) Boryl Complexes and Observations on the Interconversions between O- and C-Bound Enolates of Cu, B, and Si , 2008 .

[30]  J. S. Evans,et al.  Platinum catalysed 3,4- and 1,4-diboration of α, β-unsaturated carbonyl compounds using bis-pinacolatodiboron , 2004 .

[31]  I. Goldberg,et al.  Novel C1-Bridged Bisboronate Derivatives by Insertion of Diazoalkanes into Bis(pinacolato)diborane(4)⊥ , 2002 .

[32]  N. Miyaura,et al.  A borylcopper species generated from bis(pinacolato)diboron and its additions to α,β-unsaturated carbonyl compounds and terminal alkynes , 2001 .

[33]  N. Miyaura,et al.  Addition and Coupling Reactions of Bis(pinacolato)diboron Mediated by CuCl in the Presence of Potassium Acetate , 2000 .

[34]  Hajime Ito,et al.  Boration of an α,β-enone using a diboron promoted by a copper(I)–phosphine mixture catalyst , 2000 .

[35]  N. C. Norman,et al.  Platinum catalysed 1,4-diboration of α,β-unsaturated ketones , 1997 .

[36]  N. C. Norman,et al.  Oxidative addition of B-B bonds by rhodium(I) phosphine complexes: molecular structures of B2cat2 (cat = 1,2-O2C6H4) and its 4-But and 3,5-But2 analogs , 1994 .