VI International School On Organometallic Chemistry Marcial Moreno Mañas Instruction for Authors: Title (12 pt with initial caps, centered, bold) (one line blank) Author(s)' Name(s), Senior Author,* Underline Speaker's Name (12pt, centered, normal text) (one line blank) Affiliation(s) (italic, 12 pt, centered) e-mail address of the corresponding author (12pt, centered, normal text) (one line blank) Please read these instructions carefully and prepare your abstract using this template. (1) The abstract should be written in English using 12 pt Times New Roman font or equivalent, right-left justified, normal text, with single line spacing. (2) Each structural formulas, tables, figures, and references should be integrated in the text. (3) The deadline for submission of the abstract is April 30th, 2013. (4) The abstract should be sent as WORD files Please name the word and PDF files: your family name-first name, such as Chatani-N.doc or Chatani-N.docx (5) Schemes and Figures: ACS style. (6) References: ACS style. See examples for Invited Speakers and for other oral or poster communications For Invited Speakers (45 + 15 min lectures) a small biography and a photograph must be provided. Example: Naoto Chatani Department of Applied Chemistry, Faculty of Engineering Osaka University Suita, Osaka 565-0871, Japan Phone: +81-6879-7397, Fax: +81-6879-7396 E-mail: email@example.com Naoto Chatani studied chemistry at Osaka University and received his Ph. D. in 1984 under the guidance by Profs. Noboru Sonoda and Shinji Murai. In 1984 he joined the Institute of Scientific and Industrial Research at Osaka University and worked in the laboratory of Prof. Terukiyo Hanafusa. After postdoctoral studies (1988-1989 under Prof. Scott E. Denmark, the University of Illinois, Urbana-Champaign), he moved back to Osaka University and worked with Prof. Shinji Murai as Assistant Professor. He was promoted to Associate Professor in 1992 and Professor in 2003. His research interests center on the area of catalysis. Awards:Young Chemist Award of the Chemical Society of Japan (1991). The fourth Green and Sustainable Chemistry Award: Minister of Education, Sports, Culture, Science and Technology Prize (2005). Selected Reviews and Papers: (10.5pt) 1. “Ruthenium-Catalyzed Carbonylation at ortho C-H Bonds in Aromatic Amides Leading to Phthalimides: C-H Bond Activation Utilizing a Bidentate System”; Inoue, S.; Shiota, H.; Fukumoto, Y.; Chatani, N. J. Am. Chem. Soc. 2009, 131, 6898. 2. “Skeletal Reorganization of Enynes through Electrophilic Activation of Alkynes with Various Metal Catalysts: Double Cleavage of C-C Double Bond and Triple Bonds”; Lee, S. I.; Chatani, N. Chem. Commun. (Feature Article) 2009, 371. 3. “Rhodium-Catalyzed Reductive Cleavage of Carbon-Cyano Bonds with Hydrosilanes: A Catalytic Protocol for Removal of Cyano Groups”; Tobisu, M.; Nakamura, R.; Kita, Y.; Chatani, N. J. Am. Chem. Soc. 2009, 131, 3174. 4. “Rhodium-Catalyzed Silylation and Intramolecular Arylation of Nitriles via the Silicon-Assisted Cleavage of Carbon-Cyano Bonds”; Tobisu, M.; Kita, Y.; Ano, Y.; Chatani, N. J. Am. Chem. Soc. 2008, 130, 15982. 5. “Brønsted Acid Catalyzed Formal Insertion of Isocyanides into a C-O Bond of Acetals”; Tobisu, M.; Kitajima, A.; Yoshioka, S.; Hyodo, I.; Oshita, M.; Chatani, N. J. Am. Chem. Soc. 2007, 129, 11431. 6. “Rh(I)-Catalyzed Carbonylative Cyclization Reactions of Alkynes with 2-Bromophenylboronic Acids Leading to Indenones”; Harada, Y.; Nakanishi, J.; Fujihara, H.; Tobisu, M.; Fukumoto, Y.; Chatani, N. J. Am. Chem. Soc. 2007, 129, 5766. For Short (12+3 min), FLASH (5 min) presentations and posters: Stereoselective Synthesis of Tetrahydroisoquinolines and Tetrahydrobenzazepines from Phthalan and Isochroman Daniel García, Haythem K. Dema, Francisco Foubelo and Miguel Yus* Departamento de Química Orgánica, Facultad de Ciencias and Instituto de Síntesis Orgánica (ISO), Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain firstname.lastname@example.org, email@example.com Many tetrahydroisoquinoline1 and tetrahydrobenzazepine natural products are cytotoxic agents that display a wide range of biological activities. For these reasons, the development of new synthetic strategies which allow access to these heterocycles is of interest to the pharmaceutical industry. The stereoselective synthesis of 3-substituted 1,2,3,4-tetrahydroisoquinolines (3, n = 1) and 2-substituted 2,3,4,5-tetrahydro-1Hbenzo[d]azepine (3, n = 2) was achieved starting from phthalan (1, n = 1) or isochroman (1, n = 2) and chiral N-tert-butylsulfinyl aldimines, through a two-pot strategy: (1) Reaction of the dianionic intermediate 4 resulting from the reductive opening lithiation of phthalan2 or isochroman (1)3 with chiral aldimines in the presence of ZnMe2 to give compounds 2 with high diastereoselectivity (dr 71:29-86:14) and (2) cyclization of the aminoalcohol resulting from the removal of the tert-butylsulfinyl unit in enantiomerically pure compounds 2.4 Regarding the stereochemistry of the major stereoisomer 2, it was unambiguously determined by single X-ray analysis. Nucleophilic addition takes place to the Re-face of the imine in the case of (Rs)-sulfinylimines. Hexahydropyrroloisoquinoline 6, hexahydropyridoisoquinoline 7 and octahydrobenzopyrroloazepine 8 were accessible through this methodology starting from O-tetrahydropyranyl protected hydroxylimines 5, taking place a final double cyclization. ( )n O 1 OH O ( )n S HN 1. Li, DTBB, 0 ºC 2. ZnMe2, 20 ºC 3. RCH=NS(O)t-Bu, -65 ºC OLi ( )n Li 4 N THPO ( O S 1. HCl, MeOH, 20 ºC 2. Cl2SO, CHCl3, 50 ºC 3. NaOH/H2O, THF, 20 ºC R 2 (53-90%) N N ( )n NH R 3 (51-80%) N )m 5 6 (60%) 7 (55%) 8 (51%) m = 1, 2 n = 1, 2 R = Ph, i-Pr, CH3(CH2)7, Ph(CH2)2 1. 2. 3. 4. Scott, J. D.; Williams, R. M. Chem. Rev. 2002, 102, 1669. Almena, J.; Foubelo, F.; Yus, M., Tetrahedron 1995, 51, 3351-3364. Almena, J.; Foubelo, F.; Yus, M., Tetrahedron 1995, 51, 3365-3374. García, D.; Moreno, B.; Soler, T.; Foubelo, F.; Yus, M. Tetrahedron Lett. 2009, 50, 4710.