Synthesis and Properties of Alumoles Having an Aluminum-Halogen Bond

• Project/Area Number: 26620028
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: Tokitoh Norihiro 京都大学, 化学研究所, 教授 (90197864)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2014: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: アルミニウム / 電子不足共役系 / アルモール / アルキン / ４π電子系 / 有機典型元素化学 / 有機金属化学 / ハロゲン / 環拡大反応

Outline of Final Research Achievements

We have succeeded in the synthesis and structural determination of 1-bromo- and 1-chloroalumoles. Their reactions with nucleophiles afforded the various functionalized alumoles. We have also revealed the insertion of alkyne molecules into the Al-C bonds of the alumoles

Research Products

• [Journal Article] Reactions of Li/Cl Phosphinidenoid Complexes with 1,3,4,5-Tetramethylimidazol-2-ylidene: A New Route to N-Heterocyclic Carbene Adducts of Terminal Phosphinidene Complexes and an Unprecedented Transformation of an Oxaphosphirane Complex (2016)
  • Author(s): Klein, M.; Schnakenburg, G.; Espinosa Ferao, A.; Tokitoh, N.; Streubel, R.
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2016 Issue: 5 Pages: 685-690
  • DOI: 10.1002/ejic.201500959
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Selenium-Substituted Phosphaalkenes Obtained through 1,2-Elimination of Chlorosilanes from Selenenylchlorophosphines Obtained through 1,2-Elimination of Chlorosilanes (2016)
  • Author(s): T. Sasamori, J. M. V. Franco, J.-D. Guo, K. Sugamata, S. Nagase, R. Streubel, N. Tokitoh
  • Journal Title: Eur. J. Inorg. Chem. Volume: 2016 Issue: 5 Pages: 678-684
  • DOI: 10.1002/ejic.201500989
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Synthesis and Structure of Lewis-Base-Free Phosphinoalumane Derivatives (2016)
  • Author(s): Agou, T.; Ikeda, S.; Sasamori, T.; Tokitoh, N.
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2016 Issue: 5 Pages: 623-627
  • DOI: 10.1002/ejic.201501141
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 1,2-Dialkynyldisilanes Incorporated in 10-Membered-ring System (2015)
  • Author(s): Mizuhata, Y.; Egawa, Y.; Sasamori, T.; Tokitoh, N.
  • Journal Title: HETEROCYCLES Volume: 90 Issue: 2 Pages: 1111-1123
  • DOI: 10.3987/com-14-s(k)81
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Reaction of a Diaryldigermyne with Ethylene (2015)
  • Author(s): T. Sasamori, T. Sugahara, T. Agou, K. Sugamata, J.-D. Guo, S. Nagase, N. Tokitoh
  • Journal Title: Chem. Sci. Volume: 6 Issue: 10 Pages: 5526-5530
  • DOI: 10.1039/c5sc01266j
  • NAID: 120005753892
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Structures of a Stable Gallole Free of Lewis Base Coordination and Its Dianion (2015)
  • Author(s): T. Agou, T. Wasano, T. Sasamori, N. Tokitoh
  • Journal Title: Journal of Physical Organic Chemistry Volume: 28 Issue: 2 Pages: 104-107
  • DOI: 10.1002/poc.3344
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Oxidation of an Allene Compound Bearing 1,8-Dichloroacridene Moieties and Photolysis of the Halogenated Allene Compound for the Generation of Triplet Carbenes (2015)
  • Author(s): S.-i. Fuku-en, K. Furukawa, T. Sasamori, N. Tokitoh, M. Abe, Y. Yamamoto
  • Journal Title: J. Phys. Org. Chem Volume: 28 Issue: 2 Pages: 79-87
  • DOI: 10.1002/poc.3398
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Unexpected photochemical reactions of 2-aryl-2-ethynyltrisilane derivative (2015)
  • Author(s): Yasunobu Egawa, Yoshiyuki Mizuhata, Takahiro Sasamori, Norihiro Tokitoh
  • Journal Title: Main Group Metal Chemistry Volume: 38 Issue: 1-2 Pages: 51-55
  • DOI: 10.1515/mgmc-2014-0042
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Photochemical Properties, and Cytotoxicities of 2H-Naphtho[1,2-b]pyran and Its Photodimers (2015)
  • Author(s): Ota, M.; Sasamori, T.; Tokitoh, N.; Onodera, T.; Mizushina, Y.; Kuramochi, K.; Tsubaki, K.
  • Journal Title: The Journal of Organic Chemistry Volume: 80 Issue: 11 Pages: 5687-5695
  • DOI: 10.1021/acs.joc.5b00645
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Synthesis and Characterization of a 1,2-Digermabenzene (2015)
  • Author(s): T. Sasamori, T. Sugahara, T. Agou, J.-D. Guo, S. Nagase, R. Streubel, and N. Tokitoh
  • Journal Title: Organometallics Volume: 34 Issue: 11 Pages: 2106-2109
  • DOI: 10.1021/om501204u
  • Description: 印刷中
  • Peer Reviewed
• [Journal Article] Sulfurization of 4,5,6-Triphospha[3]Radialene (2015)
  • Author(s): Miyake, H.; Sasamori, T.; Tokitoh, N.
  • Journal Title: Phosphorus, Sulfur, and Silicon and the Related Elements Volume: 190 Issue: 8 Pages: 1247-1250
  • DOI: 10.1080/10426507.2014.991828
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Ring Expansion to 1-Bromo-1-alumacyclonona-2,4,6,8-tetraene by Insertion of Two Alkyne Molecules into the Al-C Bonds (2015)
  • Author(s): Agou, T.; Wasano, T.; Sasamori, T.; Guo, J.; Nagase, S.; Tokitoh, N.
  • Journal Title: Angewandte Chemie International Edition Volume: 54 Issue: 33 Pages: 9568-9571
  • DOI: 10.1002/anie.201504468
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Encapsulating Inorganic Acetylene, HBNH, Using Flanking Coordinative Interactions (2015)
  • Author(s): Swarnakar, A. K.; Hering-Junghans, C.; Nagata, K.; Ferguson, M. J.; McDonald, R.; Tokitoh, N.; Rivard, E.
  • Journal Title: Angewandte Chemie International Edition Volume: 54 Issue: 36 Pages: 10666-10669
  • DOI: 10.1002/anie.201504867
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Photochemical (E)-(Z) Isomerization of the P=C Double Bond in Triphospha[3]radialene-[M(CO)5] (M = W, Cr) Complexes (2015)
  • Author(s): Sasamori, T.; Hirano, K.; Miyake, H.; Tokitoh, N.
  • Journal Title: Chemistry Letters Volume: 44 Issue: 9 Pages: 1240-1242
  • DOI: 10.1246/cl.150422
  • NAID: 130005096872
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Formation of a Diaminoalkyne Derivative by Dialumane-mediated Homocoupling of t-Butyl Isocyanide (2015)
  • Author(s): Nagata, K.; Agou, T.; Sasamori, T.; Tokitoh, N.
  • Journal Title: Chemistry Letters Volume: 44 Issue: 11 Pages: 1610-1612
  • DOI: 10.1246/cl.150688
  • NAID: 130005108085
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 5-N-Arylaminothiazoles as Highly Twisted Fluorescent Monocyclic Heterocycles: Synthesis and Characterization (2015)
  • Author(s): Yamaguchi, K.; Murai, T.; Hasegawa, S.; Miwa, Y.; Kutsumizu, S.; Maruyama, T.; Sasamori, T.; Tokitoh, N.
  • Journal Title: The Journal of Organic Chemistry Volume: 80 Issue: 21 Pages: 10742-10756
  • DOI: 10.1021/acs.joc.5b01963
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Syntheses and Structures of Stable 1-Aminoalumole Derivatives (2014)
  • Author(s): 吾郷友宏、和佐野達也、笹森貴裕、時任宣博
  • Journal Title: Organometallics Volume: 33 Issue: 23 Pages: 6963-6966
  • DOI: 10.1021/om501055f
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, structure, and reactivity of a 1-bromoalumole (2014)
  • Author(s): 和佐野達也、吾郷友宏、笹森貴裕、時任宣博
  • Journal Title: Chemical Communications Volume: 50 Issue: 60 Pages: 8148-8150
  • DOI: 10.1039/c4cc03470h
  • NAID: 120005621953
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 高周期典型元素を含む新規なπ電子系の創出とその構造・性質：「重い芳香族」化合物の最近の展開 (2015)
  • Author(s): 時任宣博
  • Organizer: 015未来分子研究センター特別講演会
  • Place of Presentation: 立教大学、東京都豊島区西池袋
  • Year and Date: 2015-12-05
  • Invited
• [Presentation] Synthesis, Structures, and Properties of Stable 1,2-Disila- and 1,2-Digermabenzenes (2015)
  • Author(s): N. Tokitoh
  • Organizer: The 5th Asian Silicon Symposium (ASiS-5)
  • Place of Presentation: Jeju, Korea
  • Year and Date: 2015-10-18
  • Int'l Joint Research / Invited
• [Presentation] 高周期典型元素を含む新規なπ電子系の創出 (2015)
  • Author(s): 時任宣博
  • Organizer: 第23回触媒化学融合研究センター講演会
  • Place of Presentation: 産業技術総合研究所、茨城県つくば市
  • Year and Date: 2015-08-21
  • Invited
• [Presentation] Synthesis and Properties of Stable Alumole (2015)
  • Author(s): N. Tokitoh, T. Wasano, T. Agou and T. Sasamori
  • Organizer: The 14th International Symposium on Inorganic Ring Systems (IRIS-14)
  • Place of Presentation: Regensburg, Germany
  • Year and Date: 2015-07-26
  • Int'l Joint Research / Invited
• [Presentation] Synthesis and Properties of a Dialumene Featuring a Barrelene-type Scaffold (2015)
  • Author(s): N. Tokitoh, K. Nagata, T. Sasamori and T. Agou
  • Organizer: The 11th International Conference on Heteroatom Chemistry (ICHAC-11)
  • Place of Presentation: Caen, France
  • Year and Date: 2015-06-14
  • Int'l Joint Research / Invited
• [Presentation] １－アミノアルモール誘導体の合成と構造 (2015)
  • Author(s): 和佐野達也、吾郷友宏、笹森貴裕、時任宣博
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学（船橋市）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] ハロゲン置換アルモールの合成とアルキン類との反応 (2015)
  • Author(s): 和佐野達也、吾郷友宏、笹森貴裕、時任宣博
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学（船橋市）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Synthesis and Properties of a 1-Bromoalumole (2014)
  • Author(s): T. Agou, T. Wasano, T. Sasamori, N. Tokitoh
  • Organizer: The 26th International Conference on Organometallic Chemistry
  • Place of Presentation: Sapporo
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] Synthesis and Structure of a Gallole Dianion Bearing a Bulky Aryl Substituent (2014)
  • Author(s): N. Tokitoh, T. Agou, T. Wasano
  • Organizer: The International Symposium on Reactive Intermediates and Unusual Molecules 2014
  • Place of Presentation: Hiroshima
  • Year and Date: 2014-04-01 – 2014-04-06
  • Invited
• [Remarks] 時任研究室
  • URL: http://boc.kuicr.kyoto-u.ac.jp/www/index.html