Synthesis of Atrane-type Molecules including Group 14 Elements and Their Unique Electronic Systems

• Project/Area Number: 22550037
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Hiroshima University
• Principal Investigator: KAWACHI Atsushi 広島大学, 大学院・理学研究科, 准教授 (70260619)
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2012: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2011: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2010: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 14族元素 / アトラン分子 / ラジカル / 半結合 / スピン挙動 / 有機ケイ素化合物 / 有機亜鉛化合物 / クロスカップリング / ビフェニル化合物

Research Abstract

Tris[o-(fluorodimethylsilyl)phenyl]germylpotassium was prepared by tcleavage of the Si-Ge bond in the corresponding benzosilagermacyclobutene withKF. Reaction of the germylpotassium with dimethylchlorosilane afforded the dimethylsilylgermane. Reaction of [o-(fluorodimethylsilyl)phenyllithium with a SiCl2-carbene complex provided a novel {[o-(fluorodimethylsilyl)phenyl}chlorosilylene-carbene complex.

Research Products

• [Journal Article] Counter-Cation Effect on Reactivity of o-(Fluorodimethylsilyl)phenyl Anion (2013)
  • Author(s): Atsushi Kawachi, Takuya Teranishi, Takuma Deguchi, Yohsuke Yamamoto
  • Journal Title: Heteroatom Chem Volume: 24 Pages: 53-57
  • Peer Reviewed
• [Journal Article] Counter-Cation Effect on Reactivity of o-(Fluorodimethylsilyl)phenyl Anion (2013)
  • Author(s): Atsushi Kawachi
  • Journal Title: Heteroatom Chemistry Volume: 24 Issue: 1 Pages: 53-57
  • DOI: 10.1002/hc.21062
  • Peer Reviewed
• [Journal Article] Intramolecular H-Ar Ligand Exchange between Silicon and Boron: Functionality Transfer of Si-H to B-H (2012)
  • Author(s): Atsushi Kawachi, Hiroshi Morisaki, Norimasa Nishioka, Yohsuke Yamamoto
  • Journal Title: Chem. Asian J Volume: 7 Pages: 546-553
  • Peer Reviewed
• [Journal Article] Mechanism of Dehydrogenative Condensation of (o-Borylphenyl)hydrosilanes with Methanol (2012)
  • Author(s): Laszlo Konczol, Atsushi Kawachi, Denes Szieberth
  • Journal Title: Organometallics Volume: 31 Pages: 120-126
  • Peer Reviewed
• [Journal Article] Mechansim of Dehydrogenative Condensation of (o-Borylphenyl) hydrosilanes with Methanol (2012)
  • Author(s): Atsushi Kawachi
  • Journal Title: Organometallics Volume: 31 Issue: 1 Pages: 120-125
  • DOI: 10.1021/om2006003
  • Peer Reviewed
• [Journal Article] Intramolecular H-Ar Ligand Exchange between Silicon and Boron : Functionality Transfer of Si-H to B-H (2012)
  • Author(s): A. Kawachi, H. Morisaki, N. Nishioka, Y. Yamamoto
  • Journal Title: Chemistry-An Asian Journal Volume: 7(3) Issue: 3 Pages: 546-553
  • DOI: 10.1002/asia.201100678
  • Peer Reviewed
• [Journal Article] Ortho Magnesiation of Boron-substituted Benzenes by Using (TMP)2Mg (2011)
  • Author(s): Atsushi Kawachi, Saori Nagae, Yasuhiro Onoue, Osamu Harada, Yohsuke Yamamoto
  • Journal Title: Chem. Eur. J Volume: 29 Pages: 8005-8008
  • Peer Reviewed
• [Journal Article] Reaction of o-(HSiR2)(BMes2)C6H4with a Fluoride Ion: Fluoride Attack at Silicon and Hydride Transfer from Silicon to Boron to Form F-Si・H-B Interaction (2011)
  • Author(s): Atsushi Kawachi, Hiroshi Morisaki, Atsushi Tani, Masatoshi Zaima, Yohsuke Yamamoto
  • Journal Title: Heteroatom Chem Volume: 22 Pages: 471-475
  • Peer Reviewed
• [Journal Article] Ortho Magnesiation of Boron-substituted Benzenes by Using(TMP) 2Mg (2011)
  • Author(s): A. Kawachi, S. Nagae, Y. Onoue, O. Harada, and Y. Yamamoto
  • Journal Title: Chemistry-A European Journal Volume: 17(29) Issue: 29 Pages: 8005-8008
  • DOI: 10.1002/chem.201101022
  • Peer Reviewed
• [Journal Article] Synthesis and Structures of o-(Dihydrosilyl)- (dimesitylboryl)benzenes (2010)
  • Author(s): Atsushi Kawachi, Hiroshi Morisaki, Masatoshi Zaima, Takuya Teranishi, Yohsuke Yamamoto
  • Journal Title: J. Organomet. Chem. Volume: 695 Pages: 2167-2171
  • Peer Reviewed
• [Journal Article] Synthesis, structure and reactions of triarylgermyl anion with ambiphilic character (2010)
  • Author(s): Atsushi Kawachi, Koji Machida, and Yohsuke Yamamoto
  • Journal Title: Chem. Commun. Volume: 46 Pages: 1890-1892
  • Peer Reviewed
• [Journal Article] Reaction of o-(HSiR_2)(BMes_2)C_6H_4 with a Fluoride Ion : Fluoride Attack at Silicon and Hydride Transfer from Silicon to Boron to Form F-Si…H-B Interaction (2010)
  • Author(s): Atsushi Kawachi
  • Journal Title: Journal of Organometallic Chemistry Volume: 695 Pages: 2167-2171
  • Peer Reviewed
• [Journal Article] Synthesis and Structures of o-(Dihydrosilyl)(dimesitylboryl)benzenes (2010)
  • Author(s): Atsushi Kawachi
  • Journal Title: Chemical Communication Volume: 46 Pages: 1890-1892
  • Peer Reviewed
• [Presentation] ケイ素官能性ジベンゾシラボリンの合成,構造および反応 (2013)
  • Author(s): 廣藤龍哉,河内敦,山本陽介
  • Organizer: 日本化学会第92 春季年会
  • Place of Presentation: 慶応大学(神奈川県横浜市)
  • Year and Date: 2013-03-28
• [Presentation] 分子内B-H/C-H 脱水素化による含ホウ素環状化合物の合成 (2013)
  • Author(s): 植木幸広,河内敦,山本陽介
  • Organizer: 日本化学会第92 春季年会
  • Place of Presentation: 慶応大学(神奈川県横浜市)
  • Year and Date: 2013-03-28
• [Presentation] ケイ素官能性ジベンゾシラボリンの合成と反応 (2013)
  • Author(s): 廣藤龍哉,河内敦,山本陽介
  • Organizer: 日本化学会第93 春季年会
  • Place of Presentation: 立命館大学(滋賀県草津市)
  • Year and Date: 2013-03-25
• [Presentation] H-Ar交換反応およびB-H/C-H脱水素化によるジベンゾシラボリンの合成と反応 (2013)
  • Author(s): 河内敦
  • Organizer: 有機合成化学協会中国四国支部第28若手化学道場
  • Place of Presentation: 島根県立青少年の家
  • Invited
• [Presentation] ケイ素官能性ジベンゾシラボリンの合成と反応 (2013)
  • Author(s): 廣藤龍哉
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学草津キャンパス
• [Presentation] Formation, Structures, and Reactions of Dibenzosilaborins (2013)
  • Author(s): 河内敦
  • Organizer: The 10th International Conference on Heteroatom Chemistry
  • Place of Presentation: 京都大学化学研究所
• [Presentation] Formation, Structures and Reactions of Silicon-Functionalized Dibenzosilaborins (2013)
  • Author(s): 廣藤龍哉
  • Organizer: 4th Asian Silicon Symposium
  • Place of Presentation: 茨城県つくば市
• [Presentation] Formation, Structures and Reactions of Silicon- Functionalized Dibenzosilaborins (2012)
  • Author(s): Tatsuya Hirofuji, Hiroshi Morisaki, Atsushi Kawachi, Yohsuke Yamamoto
  • Organizer: 4th Asian Silicon Symposium
  • Place of Presentation: Tsukuba, Japan.
  • Year and Date: 2012-10-24
• [Presentation] H-Ar 交換反応および B-H/C-H 脱水素化によるジベンゾシラボリンの合成と反応 (2012)
  • Author(s): 河内敦
  • Organizer: 有機合成化学協会中国四国支部第28若手化学道場
  • Place of Presentation: 島根県立青少年の家(島根県出雲市)
  • Year and Date: 2012-09-08
• [Presentation] Formation, Structures, and Reactions of Dibenzosilaborins (2012)
  • Author(s): Atushi Kawachi, Hiroshi Morisaki, Tatsuya Hirofuji, Yukihiro Ueki, Yohsuke Yamamoto
  • Organizer: The 10th International Conference on Heteroatom Chemistry
  • Place of Presentation: Uji, Kyoto, Japan
  • Year and Date: 2012-05-25
• [Presentation] ケイ素-水素結合およびケイ素-フッ素結合の反応性制御と新規 14 族元素化合物の合成 (2012)
  • Author(s): 河内敦
  • Organizer: 有機合成化学協会中国四国支部第67 パネル討論会
  • Place of Presentation: 広島大学理学部(広島県東広島市)
  • Year and Date: 2012-05-19
• [Presentation] ケイ素官能性ジベンゾシラボリンの合成,構造および反応 (2012)
  • Author(s): 廣藤龍哉
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学(神奈川県横浜市)
  • Year and Date: 2012-03-27
• [Presentation] 分子内B-H/C-H脱水素化による含ホウ素環状化合物の合成 (2012)
  • Author(s): 植木幸広
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学(神奈川県横浜市)
  • Year and Date: 2012-03-27
• [Presentation] Ortho Magnesiation of Boron-substituted Benzenes Using (TMP)_2Mg (2011)
  • Author(s): 河内敦
  • Organizer: 第1回分子活性化に関する国際会議
  • Place of Presentation: 淡路(兵庫県)
  • Year and Date: 2011-11-09
• [Presentation] ケイ素原子とホウ素原子との間の水素-アリール基交換反応についての理論的研究 (2011)
  • Author(s): 河内敦,森崎宏,山本陽介
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋大学(愛知県名古屋市)
  • Year and Date: 2011-09-09
• [Presentation] H-Ar Ligand Exchange between Silicon and Boron in o-(Hydrosilyl)- (diarylboryl)benzenes and Subsequent Intramolecular Cyclization: Formation of Dibenzosilaborins (2011)
  • Author(s): Atsushi Kawachi, Hiroshi Morisaki, Yohsuke Yamamoto
  • Organizer: 16th International Symposium on Silicon Chemistry
  • Place of Presentation: Hamilton, Ontario, Canada.
  • Year and Date: 2011-08-18
• [Presentation] H-Ar Ligand Exchange between Silicon and Boron in o-(Hydrosilyl) (diaryloryl)benzenes and Subsequent Intramolecular Cyclization : Formation of Dibenzosilaborins (2011)
  • Author(s): 河内敦
  • Organizer: 第16回ケイ素化学国際会議
  • Place of Presentation: ハミルトン(カナダ)
  • Year and Date: 2011-08-16
• [Presentation] ホウ素原子置換ベンゼンのオルトマグネシオ化反応:オルトマグネシオ体のX線結晶構造解析 (2011)
  • Author(s): 河内敦,長江沙織,原田理,山本陽介
  • Organizer: 日本化学会第91 春季年会
  • Place of Presentation: 神奈川大学(神奈川県横浜市).
  • Year and Date: 2011-03-29
• [Presentation] o-ヒドロシリル(ボリル)ベンゼンの分子内環化によるジベンゾシラボリンの合成 (2011)
  • Author(s): 森崎宏,河内敦,山本陽介
  • Organizer: 日本化学会第91 春季年会
  • Place of Presentation: 神奈川大学(神奈川県横浜市).
  • Year and Date: 2011-03-29
• [Presentation] ホウ素原子置換ベンゼンのオルトマグネシオ化反応:オルトマグネシオ体のX線結晶構造解析 (2011)
  • Author(s): 河内敦
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜市)
  • Year and Date: 2011-03-27
• [Presentation] O-ヒドロシリル(ボリル)ベンゼンの分子内環化によるジベンゾシラボリンの合成 (2011)
  • Author(s): 森崎宏
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜市)
  • Year and Date: 2011-03-26
• [Presentation] 二つのホスホニウムメチリドを分子内炭素配位子とする 5 配位ケイ素化合物の合成研究 (2010)
  • Author(s): 石部徹,河内敦,山本陽介
  • Organizer: 第37回有機典型元素化学討論会
  • Place of Presentation: 室蘭市民会館(北海道室蘭市)
  • Year and Date: 2010-11-27
• [Presentation] 二つのホスホニウムメチリドを分子内炭素配位子とする5配位ケイ素化合物の合成研究 (2010)
  • Author(s): 石部徹
  • Organizer: 第37回有機典型元素化学討論会
  • Place of Presentation: 室蘭市民会館(室蘭市)
  • Year and Date: 2010-11-25
• [Presentation] o-(フルオロシリル)フェニルメタル化合物の合成・構造・反応 (2010)
  • Author(s): 河内敦
  • Organizer: 第14回ケイ素化学協会シンポジウム
  • Place of Presentation: ニューウェルシティー湯河原(静岡県熱海市).
  • Year and Date: 2010-11-20
• [Presentation] o-(フルオロシリル)フェニルメタル化合物の合成・構造・反応 (2010)
  • Author(s): 河内敦
  • Organizer: 第14回ケイ素化学協会シンポジウム
  • Place of Presentation: ニューウェルシティー湯河原(熱海市)
  • Year and Date: 2010-11-20
• [Presentation] o-ジヒドロシリル(ジメシチルボリル)ベンゼンの合成と反応 (2010)
  • Author(s): 森崎宏,河内敦,山本陽介
  • Organizer: 第57回有機金属化学討論会
  • Place of Presentation: 中央大学(東京都八王子市).
  • Year and Date: 2010-09-11
• [Presentation] o-ジヒドロシリル(ジメシチルボリル)ベンゼンの合成と反応 (2010)
  • Author(s): 森崎宏
  • Organizer: 第57有機金属化学討論会
  • Place of Presentation: 中央大学(八王子市)
  • Year and Date: 2010-09-11
• [Presentation] Ortho Magnesiation of Boron-substituted Benzenes Using (TMP)2Mg (2010)
  • Author(s): Atsushi Kawachi, Saori Nagae, Yasuhiro Onoue, Yohsuke Yamamoto
  • Organizer: 9th International Symposium on Carbanion Chemistry
  • Place of Presentation: Florence, Italy
  • Year and Date: 2010-07-24
• [Presentation] Ortho Magnesiation of Boron-substituted Benzenes Using (TMP)_2Mg (2010)
  • Author(s): 河内敦
  • Organizer: 第9回カルボアニオン化学に関する国際会議
  • Place of Presentation: フィレンツエ(イタリア)
  • Year and Date: 2010-07-21
• [Presentation] ケイ素―水素結合およびケイ素―フッ素結合の反応性制御と新規14族元素化合物の合成
  • Author(s): 河内敦
  • Organizer: 有機合成化学協会中国四国支部第67パネル討論会
  • Place of Presentation: 広島大学理学部
  • Invited
• [Remarks]
  • URL: http:////home.hiroshima-u.ac.jp/hetero2/
• [Remarks]
  • URL: http://home.hiroshima-u.ac.jp/hetero/
• [Remarks]
  • URL: http://home.hiroshima-u.ac.jp/hetero/top.html