Gold-catalyzed [5+2] cycloaddition of quinolinium zwitterions and allenamides as an efficient route to fused 1,4-diazepines.

Herein, we demonstrate a new catalytic cycloaddition of quinolinium zwitterions involving a gold-bound allylic cation intermediate. This ligand-free higher-order cycloaddition efficiently affords a variety of fused 1,4-diazepine derivatives in a stereospecific manner at room temperature.

[1]  E. Yoo,et al.  Recent Advances in the Catalytic Cycloaddition of 1,n-Dipoles , 2018 .

[2]  E. Yoo,et al.  Synthesis of Fused Polycyclic 1,4-Benzodiazepines via Metal-Free Cascade [5 + 2]/[2 + 2] Cycloadditions. , 2017, Organic letters.

[3]  J. Mascareñas,et al.  Gold(I)-Catalyzed Enantioselective [2+2+2] Cycloadditions: An Expedient Entry to Enantioenriched Tetrahydropyran Scaffolds , 2017 .

[4]  Rai‐Shung Liu,et al.  Gold-catalyzed [3+2]-annulations of α-aryl diazonitriles with ynamides and allenamides to yield 1-amino-1H-indenes. , 2016, Chemical communications.

[5]  Junliang Zhang,et al.  Enantioselective gold-catalyzed intermolecular [2 + 2]-cycloadditions of 3-styrylindoles with N-allenyl oxazolidinone , 2016 .

[6]  E. Yoo,et al.  Rhodium(II)-Catalyzed Cycloaddition Reactions of Non-classical 1,5-Dipoles for the Formation of Eight-Membered Heterocycles. , 2015, Angewandte Chemie.

[7]  Rai‐Shung Liu,et al.  Diversity in Gold-Catalyzed Formal Cycloadditions of Ynamides with Azidoalkenes or 2H-Azirines: [3+2] versus [4+3] Cycloadditions. , 2015, Chemistry.

[8]  Junliang Zhang,et al.  Transfer of chirality in the rhodium-catalyzed intramolecular formal hetero-[5 + 2] cycloaddition of vinyl aziridines and alkynes: stereoselective synthesis of fused azepine derivatives. , 2015, Journal of the American Chemical Society.

[9]  M. Bandini,et al.  Enantioselective gold catalyzed dearomative [2+2]-cycloaddition between indoles and allenamides. , 2015, Chemical communications.

[10]  E. Yoo,et al.  Multicomponent [5 + 2] cycloaddition reaction for the synthesis of 1,4-diazepines: isolation and reactivity of azomethine ylides. , 2014, Journal of the American Chemical Society.

[11]  J. Mascareñas,et al.  [4+2] and [4+3] catalytic cycloadditions of allenes. , 2014, Chemical Society reviews.

[12]  J. Mascareñas,et al.  Straightforward assembly of benzoxepines by means of a rhodium(III)-catalyzed C-H functionalization of o-vinylphenols. , 2014, Journal of the American Chemical Society.

[13]  N. Iqbal,et al.  Gold(I)-catalyzed benz[c]azepin-4-ol synthesis by intermolecular [5 + 2] cycloaddition. , 2013, The Journal of organic chemistry.

[14]  J. Mascareñas,et al.  Gold(I)-catalyzed cascade cycloadditions between allenamides and carbonyl-tethered alkenes: an enantioselective approach to oxa-bridged medium-sized carbocycles. , 2013, Angewandte Chemie.

[15]  J. Stryker,et al.  [5 + 2] cycloaddition reactions in organic and natural product synthesis. , 2013, Chemical reviews.

[16]  Samuel Suárez‐Pantiga,et al.  Intermolecular [2+2] reaction of N-allenylsulfonamides with vinylarenes: enantioselective gold(i)-catalyzed synthesis of cyclobutane derivatives. , 2012, Angewandte Chemie.

[17]  J. Mascareñas,et al.  Axially chiral triazoloisoquinolin-3-ylidene ligands in gold(I)-catalyzed asymmetric intermolecular (4 + 2) cycloadditions of allenamides and dienes. , 2012, Journal of the American Chemical Society.

[18]  J. Mascareñas,et al.  Gold(I)-Catalyzed Intermolecular [2+2] Cycloadditions between Allenamides and Alkenes , 2012 .

[19]  Samuel Suárez‐Pantiga,et al.  Phosphite‐Gold(I)‐Catalyzed [2+2] Intermolecular Cycloaddition of Enol Ethers with N‐Allenylsulfonamides , 2012 .

[20]  C. Nevado,et al.  Gold-Containing and Gold-Generated 1,n-Dipoles as Useful Platforms Toward Cycloadditions and Cyclizations , 2012 .

[21]  Xiao-Xiao Li,et al.  Formal intermolecular [2 + 2] cycloaddition reaction of allenamide [corrected] with alkenes via gold catalysis. , 2012, Organic letters.

[22]  J. Mascareñas,et al.  Recent developments in gold-catalyzed cycloaddition reactions , 2011, Beilstein journal of organic chemistry.

[23]  J. Mascareñas,et al.  Gold(I)-catalyzed intermolecular (4 + 2) cycloaddition of allenamides and acyclic dienes , 2011 .

[24]  H. Pellissier.  Recent Developments in the [5+2] Cycloaddition , 2011 .

[25]  M. Harmata.  The (4+3)-cycloaddition reaction: simple allylic cations as dienophiles. , 2010, Chemical communications.

[26]  J. Takaya,et al.  Intermolecular 1,5-dipolar cycloaddition reaction of tungsten-containing vinylazomethine ylides leading to seven-membered heterocycles. , 2006, Organic letters.

[27]  J. Cryan,et al.  Altered response to benzodiazepine anxiolytics in mice lacking GABA B(1) receptors. , 2004, European journal of pharmacology.

[28]  E. Sigel,et al.  On the Benzodiazepine Binding Pocket in GABAA Receptors* , 2004, Journal of Biological Chemistry.

[29]  P. Rashatasakhon,et al.  Cycloaddition Reactions of Vinyl Oxocarbenium Ions , 2003 .

[30]  J. Frisvad,et al.  UV-guided screening of benzodiazepine producing species in Penicillium. , 2000, Biochemical systematics and ecology.

[31]  Rahbaek,et al.  Circumdatins D, E, and F: further fungal benzodiazepine analogues from aspergillus ochraceus , 1999, Journal of natural products.

[32]  Joshi,et al.  Sclerotigenin: A new antiinsectan benzodiazepine from the sclerotia of penicillium sclerotigenum , 1999, Journal of natural products.

[33]  J. Frisvad,et al.  Circumdatin A, B, and C: Three New Benzodiazepine Alkaloids Isolated from a Culture of the Fungus Aspergillus ochraceus. , 1999, The Journal of organic chemistry.

[34]  B. Foxman,et al.  Total Syntheses of (−)-Asperlicin and (−)-Asperlicin C , 1998 .

[35]  C. Barrow,et al.  Benzomalvins, new substance P inhibitors from a Penicillium sp. , 1994, The Journal of antibiotics.

[36]  R. Chang,et al.  Asperlicin, a novel non-peptidal cholecystokinin antagonist from Aspergillus alliaceus. Fermentation, isolation and biological properties. , 1985, The Journal of antibiotics.

[37]  R. N. Brogden,et al.  Triazolam: A Review of its Pharmacological Properties and Therapeutic Efficacy in Patients with Insomnia , 1981, Drugs.

[38]  H. Mohler,et al.  Benzodiazepine receptor: demonstration in the central nervous system , 1977, Science.

[39]  L. Sternbach,et al.  Chemistry of benzodiazepines , 1968 .

[40]  Junliang Zhang,et al.  Enantioselective Gold‐Catalyzed Intermolecular [2 + 2] versus [4 + 2]‐Cycloadditions of 3‐Styrylindoles with N‐Allenamides: Observation of Interesting Substituent Effects. , 2016 .

[41]  H. Hoffmann,et al.  [4+3] cycloadducts from Lewis acid mediated reactions of acroleins with cyclopentadiene. , 2004, Angewandte Chemie.

[42]  M. Butler,et al.  Circumdatin G, a new alkaloid from the fungus Aspergillus ochraceus. , 2001, Journal of natural products.

[43]  A. Hosomi,et al.  [4 + 3] Cycloadditions , 1991 .

[44]  L. Sternbach.  1,4-benzodiazepines. Chemistry and some aspects of the structure-activity relationship. , 1971, Angewandte Chemie.