Development of Stereoselective Formation of Carbon-Halogen Bonds

• Project/Area Number: 24655032
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: KAMBE Nobuaki 大阪大学, 工学(系)研究科(研究院), 教授 (60144432)
• Co-Investigator(Kenkyū-buntansha): IWASAKI Takanori 大阪大学, 大学院工学研究科, 助教 (50550125)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2013: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2012: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 不斉触媒 / 有機触媒 / ハロゲン化

Research Abstract

A new asymmetric synthesis of chiral organo halides from the corresponding racemic alcohols through stereo retention from an enantiomer and inversion for the other one was investigated. Initial study using enantiomerically pure phenethyl alcohol and various amine nucleophiles revealed that the enantioselectivities largely depended on the structure of the amine nucleophiles, suggesting that the present approach can be a potent new methodology for asymmetric halogenation of alcohols.
We tested various chiral organocatalysts and found that some chiral pyridine and phosphine based organocatalysts showed moderate enantioselectivities for the chlorination of racemic alcohols.

Research Products

• [Journal Article] Co-Catalyzed Cross-Coupling of Alkyl Halides with Tertiary Alkyl Grignard Reagents Using a 1,3-Butadiene Additive (2013)
  • Author(s): T.Iwasaki, H.Takagawa, S.P.Singh, H.Kuniyasu, N.Kambe
  • Journal Title: J. Am. Chem. Soc. Volume: 135(26) Issue: 26 Pages: 9604-9607
  • DOI: 10.1021/ja404285b
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Intermolecular Oxidative Cross-Coupling of (Hetero) Arenes with Chalcogenophenes (2013)
  • Author(s): Vutukuri Prakash Reddy
  • Journal Title: Organic Letters Volume: 15 Issue: 6 Pages: 1290-1293
  • DOI: 10.1021/ol400230y
  • Peer Reviewed
• [Journal Article] Ni-Butadiene Catalytic System for the Cross-Coupling of Bromoalkanoic Acids with Alkyl Grignard Reagents : A Practical and Versatile Method for Preparing Fatty Acids (2013)
  • Author(s): Takanori Iwasaki
  • Journal Title: Chemistry A European Journal Volume: 19 Issue: 9 Pages: 2956-2960
  • DOI: 10.1002/chem.201204222
  • Peer Reviewed
• [Journal Article] The Nickel Catalyzed Coupling of Thiomethyl-Substituted 1, 3-Benzothiazoles with Secondary Alkyl Grignard Reagents (2013)
  • Author(s): Ghaderi, A, Iwasaki, T, Fukuoka, A, Terao, J, Kambe, N.
  • Journal Title: CHEMISTRY A EUROPEAN JOURNAL Volume: (In press) Issue: 9 Pages: 2951-2955
  • DOI: 10.1002/chem.201203413
  • Peer Reviewed
• [Journal Article] Copper-Catalyzed Coupling Reaction of Unactivated Secondary Alkyl Iodides with Alkyl Grignard Reagents in the Presence of 1,3-Butadiene as an Effective Additive (2012)
  • Author(s): R.Shen, T.Iwasaki, J.Terao, N.Kambe
  • Journal Title: Chem. Commun. Volume: 48(47) Issue: 74 Pages: 9313-9615
  • DOI: 10.1039/c2cc34847k
  • Peer Reviewed
• [Presentation] 第9族金属アニオン錯体を鍵活性種とする炭素―炭素結合形成反応 (2014)
  • Author(s): 岩﨑孝紀
  • Organizer: 日本化学会第94春季年会Reaxys Prize Club Symposium in Japan 2014
  • Place of Presentation: 名古屋大学
  • Invited
• [Presentation] Co-Catalyzed Cross-Coupling of Alkyl Halides with Tertiary Alkyl Grignard Reagents Using a 1,3-Butadiene Additive (2014)
  • Author(s): Takanori Iwasaki, Hiroaki Takagawa, Surya P. Singh, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] 銅触媒を用いたα，β―アセチレニックエステルのヒドロフッ素化反応 (2014)
  • Author(s): 中﨑雅人、国安均、真川敦嗣、岩﨑孝紀、 Bobuatong, Karan、江原正博、神戸宣明
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] ロジウム触媒を用いたビニルエーテル類とアリールグリニャール試薬とのクロスカップリング反応 (2014)
  • Author(s): 秋本 諒・宮田佳典・岩﨑孝紀・国安 均・神戸宣明
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] Cross-Coupling of Tertiary Alkyl Grignard Reagents with Alkyl Halides Catalyzed by Cobalt Using 1,3-Butadiene as an Additive (2013)
  • Author(s): T. Iwasaki, H. Takagawa, S. P. Singh, H. Kuniyasu, N. Kambe
  • Organizer: 10th International Symposium on Carbanion Chemistry (ISCC-10)
  • Place of Presentation: 京都府
  • Year and Date: 2013-09-14
• [Presentation] 遷移金属触媒による2級および3級炭素上でのクロスカップリング反応 (2013)
  • Author(s): 岩﨑孝紀、高川裕章、沈如偉、寺尾潤、国安均、神戸宣明
  • Organizer: 第103回有機合成シンポジウム
  • Place of Presentation: 東京都(慶應義塾大学)
  • Year and Date: 2013-06-06
• [Presentation] Pd/Xantphos触媒存在下、CsF/ArI/18-crown-6を用いたアレン類のアリールフッ素化反応 (2013)
  • Author(s): 若狭崇志・国安 均・真川敦嗣・岩﨑孝紀・ 神戸宣明
  • Organizer: 石油学会関西支部 第22回研究発表会
  • Place of Presentation: 近畿大学
• [Presentation] シクロデキストリンの不斉場を利用したロジウム触媒によるアリールボロン酸のエノン類へのエナンチオ選択的1,4-付加反応 (2013)
  • Author(s): 高橋亮太、津田 進、岩﨑孝紀、朝日 薫、藤原 眞一、国安 均、神戸宣明
  • Organizer: 第40回有機典型元素化学討論会
  • Place of Presentation: 近畿大学
• [Presentation] Mechanistic Insight into the Rh-Catalyzed Cross-Coupling of Vinyl Ethers with Grignard Reagents (2013)
  • Author(s): Takanori Iwasaki, Yoshinori Miyata, Yuya Komatsu, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: The Eighth International Symposium on Integrated Synthesis (ISIS-8)
  • Place of Presentation: 東大寺
• [Presentation] Enantioselective 1.4-Additon of Arylboronic Acids to Enones Catalyzed by Rh-NHC Complexes Bearing a Cyclodextrin (2013)
  • Author(s): Ryota Takahashi, Susumu Tsuda, Takanori Iwasaki, Kaoru Asahi, Shin-ichi Fujiwara, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: Novel Designed Surface and Catalysis for Greener Future: C&FC Pre-Symposium in Himeji
  • Place of Presentation: イーグレ姫路
• [Presentation] コバルト触媒を用いた三級アルキルグリニャール試薬とアルキルハライドとのクロスカップリング反応 (2013)
  • Author(s): 岩﨑孝紀、高川裕章、Singh, Surya P.、国安均、神戸宣明
  • Organizer: 第39回反応と合成の進歩シンポジウム
  • Place of Presentation: 九州大学
• [Presentation] 銅触媒を用いる効率的sp3炭素間結合形成反応－触媒効率と不飽和炭化水素配位子の役割― (2013)
  • Author(s): 今西怜子、清水良平、岩﨑孝紀、寺尾 潤、国安 均、神戸宣明
  • Organizer: 第3回CSJ化学フェスタ2013 ―日本化学会秋季事業―
  • Place of Presentation: タワーホール船堀
• [Presentation] ニッケル触媒を用いたC-F結合切断を伴う多成分カップリング反応 (2013)
  • Author(s): 福岡明日香、岩﨑孝紀、寺尾 潤、国安 均、神戸宣明
  • Organizer: 第3回CSJ化学フェスタ2013 ―日本化学会秋季事業―
  • Place of Presentation: タワーホール船堀
• [Presentation] Nickel-Catalyzed Multicomponent Coupling Reaction through C-F Bond Cleavage (2013)
  • Author(s): Asuka Fukuoka, Takanori Iwasaki, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 10th International Symposium on Carbanion Chemistry (ISCC-10)
  • Place of Presentation: 同志社大学
• [Presentation] Cross-Coupling of Tertiary Alkyl Grignard Reagents with Alkyl Halides Catalyzed by Cobalt Using 1,3-Butadiene as an Additive (2013)
  • Author(s): Takanori Iwasaki, Hiroaki Takagawa, Surya P. Singh, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 10th International Symposium on Carbanion Chemistry (ISCC-10)
  • Place of Presentation: 同志社大学
• [Presentation] 銅触媒を用いるアルキル－アルキルクロスカップリング反応－触媒効率と不飽和炭化水素配位子の役割 (2013)
  • Author(s): 今西怜子、清水良平、岩﨑孝紀、国安 均、神戸宣明
  • Organizer: 第60回有機金属化学討論会
  • Place of Presentation: 学習院大学
• [Presentation] Pd/Xantphos触媒存在下、CsF/ArI/18-crown-6を用いたアレン類のアリールフッ素化反応 (2013)
  • Author(s): 若狭崇志・国安 均・真川敦嗣・岩﨑孝紀・ 神戸宣明
  • Organizer: 第60回有機金属化学討論会
  • Place of Presentation: 学習院大学
• [Presentation] CD連結NHC配位子－ロジウム触媒によるエノン類へのアリールボロン酸の1,4-付加反応－生成物キラリティーの反転 (2013)
  • Author(s): 高橋亮太、津田 進、岩﨑孝紀、朝日 薫、藤原 眞一、国安 均、神戸宣明
  • Organizer: 第30回シクロデキストリンシンポジウム
  • Place of Presentation: くまもと県民交流館パレア
• [Presentation] Co-catalyzed cross-coupling of alkyl halides with alkyl Grignard reagents (2013)
  • Author(s): Takanori Iwasaki, Hiroaki Takagawa, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC-16)
  • Place of Presentation: 北海道大学
• [Presentation] Nickel-Catalyzed Four-Component Coupling Reaction of 1,3-Butadiene, Alkyl Fluorides and Aryl Grignard Reagents Through Dimerization of 1,3-Butadiene (2013)
  • Author(s): Asuka Fukuoka, Takanori Iwasaki, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 20th International Symposium on Olefin Metathesis and Related Chemistry (ISOM-20)
  • Place of Presentation: 東大寺
• [Presentation] Highly Effective Copper-Catalyzed sp3(C)-sp3(C) Bond Forming Reaction (2013)
  • Author(s): Reiko Imanishi, Ryohei Shimizu, Takanori Iwasaki, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 20th International Symposium on Olefin Metathesis and Related Chemistry (ISOM-20)
  • Place of Presentation: 東大寺
• [Presentation] Co-Catalyzed Cross-Coupling of Alkyl Halides with Tertiary Alkyl Grignard Reagents Using a 1,3-Butadiene Additive (2013)
  • Author(s): Takanori Iwasaki, Hiroaki Takagawa, Surya P. Singh, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 20th International Symposium on Olefin Metathesis and Related Chemistry (ISOM-20)
  • Place of Presentation: 東大寺
• [Presentation] 銅触媒を用いたアルキンのヒドロフッ素化反応 (2013)
  • Author(s): 中﨑雅人、真川敦嗣、岩﨑孝紀、国安 均、神戸宣明
  • Organizer: 第46回有機金属若手の会 夏の学校
  • Place of Presentation: 宮城蔵王ロイヤルホテル
• [Presentation] 高活性銅触媒によるアルキル―アルキルクロスカップリング反応 (2013)
  • Author(s): 岩﨑孝紀、今西怜子、清水良平、寺尾潤、国安均、神戸宣明
  • Organizer: 第2回JACI/GSCシンポジウム
  • Place of Presentation: メルパルク大阪
• [Presentation] 遷移金属触媒による2級および3級炭素上でのクロスカップリング反応 (2013)
  • Author(s): 岩﨑孝紀、高川裕章、沈如偉、寺尾潤、国安均、神戸宣明
  • Organizer: 第103回有機合成シンポジウム
  • Place of Presentation: 慶應義塾大学
• [Presentation] Co-catalyzed cross-coupling of alkyl halides with alkyl Grignard reagents (2013)
  • Author(s): Takanori Iwasaki, Hiroaki Takagawa, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 5th Gratama Workshop
  • Place of Presentation: 東京工業大学
• [Presentation] Nickel-Catalyzed Four-Component Coupling Reaction of 1,3-Butadiene, Alkyl Fluorides and Aryl Grignard Reagents through Dimerization of 1,3-Butadiene (2013)
  • Author(s): Asuka Fukuoka, Takanori Iwasaki, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: 5th Gratama Workshop
  • Place of Presentation: 東京工業大学
• [Presentation] シクロデキストリンが連結されたNHC配位子を用いたロジウム触媒によるアルデヒドの不斉アリール化反応 (2012)
  • Author(s): 朝日薫、津田進、岩崎孝紀、藤原眞一、国安均、神戸宣明
  • Organizer: 第59回有機金属化学討論会
  • Place of Presentation: 大阪(大阪大学吹田キャンパス)ポスター賞受賞
  • Year and Date: 2012-09-14
• [Presentation] 1,3-ブタジエン存在下、銅触媒による活性化されていない2級アルキルヨージドとアルキルグリニャール試薬とのクロスカップリング反応 (2012)
  • Author(s): 岩﨑孝紀・沈如偉・寺尾潤・国安均・神戸宣明
  • Organizer: 第59回有機金属化学討論会
  • Place of Presentation: 大阪
• [Presentation] 銅触媒による二級ハロゲン化アルキルのアルキル化およびブタジエンの1,2-ヒドロアルキル化による三級炭素中心の構築 (2012)
  • Author(s): 岩﨑孝紀・清水良平・沈如偉・寺尾潤・国安均・神戸宣明
  • Organizer: 石油学会２０１２年秋田大会
  • Place of Presentation: 秋田
• [Presentation] コバルト触媒を用いた炭素－ハロゲン結合の切断を伴う炭素－炭素結合形成反応 (2012)
  • Author(s): 高川裕章・Surya Prakash Singh・岩﨑孝紀・寺尾潤・国安均・神戸宣明
  • Organizer: 第39回有機典型元素化学討論会
  • Place of Presentation: 岩手
• [Presentation] Cu-catalyzed cross-coupling reaction at secondary carbon centers using haloalkanes (2012)
  • Author(s): Takanori Iwasaki, Ryohei Shimizu, Ruwei Shen, Jen Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: The 10th International Conference on Heteroatom Chemistry (ICHAC-10)
  • Place of Presentation: 京都
• [Presentation] Highly Effective Copper-Catalyzed Cross-Coupling Reaction of Alkyl Halides with Alkyl Grignard Reagents (2012)
  • Author(s): Reiko Imanishi, Ryohei Shimizu, Takanori Iwasaki, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: The Twelfth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
  • Place of Presentation: 京都
• [Presentation] Cobalt-Catalyzed Cross-Coupling Reaction of Alkyl Halides with Tertiary Alkyl Grignard Reagents in the Presence of Conjugated Diene as an Additive (2012)
  • Author(s): Hiroaki Takagawa, Surya Prakash Singh, Takanori Iwasaki, Jun Terao, Hitoshi Kuniyasu, Nobuaki Kambe
  • Organizer: The Twelfth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
  • Place of Presentation: 京都
• [Book] Coupling Reaction Between sp^3-Carbon Centers, Comprehensive Organic Synthesis II (Second Edition)(P. Knochel, G. A. Molander Eds) (2014)
  • Author(s): T. Iwasaki, N. Kambe
  • Publisher: Elsevier
• [Remarks]
  • URL: http://www.chem.eng.osaka-u.ac.jp/~catsyn/index.html