Integrated Synthesis by Designed Reaction Field

• Project Area: Middle molecular strategy: Creation of higher bio-functional molecules by integrated synthesis.
• Project/Area Number: 15H05848
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Osaka University
• Principal Investigator: Yasuda Makoto 大阪大学, 工学研究科, 教授 (40273601)
• Project Period (FY): 2015-06-29 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥45,500,000 (Direct Cost: ¥35,000,000、Indirect Cost: ¥10,500,000); Fiscal Year 2019: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000); Fiscal Year 2018: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000); Fiscal Year 2017: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000); Fiscal Year 2016: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000); Fiscal Year 2015: ¥10,140,000 (Direct Cost: ¥7,800,000、Indirect Cost: ¥2,340,000)
• Keywords: 合成化学 / 有機化学 / 錯体化学 / 触媒 / 選択的反応 / 触媒化学 / ルイス酸

Outline of Final Research Achievements

The metal complexes with organic framework surrounding around the metal center were synthesized. They were applied to the catalytic reactions in which the metal complexes act as a catalyst to recognize aromatic compounds. The pi-pocket around the metal center recognized the aromatic moiety of the substrate over aliphatic ones. The complex can be tuned by through-space interaction between organic frame work and metal center that are not bound in covalent bond. The aluminum-cage shaped complex with bromine atoms at ortho positions in pi-pocket moieties catalyzed beta-selective glycosylation at room temperature. The moderate Lewis acidity and appropriate steric hindrance enabled a high selectivity at rt.
Indium-catalyzed reaction gave the coupling product to give diarylethylene derivatives that led to new type of hydrocarbon compounds with anti-aromaticity and open-shell characters in one molecule. Other types of metal catalyzed reaction based on carbometallation have been developed.

Academic Significance and Societal Importance of the Research Achievements

金属触媒はその金属自身の反応性に依存した触媒活性を示すため、その利用に大きな制限がある。一方で有機化合物は自在に有機合成によりデザインが多様である。この有機骨格を金属に付与することで、精密に性状を制御した金属触媒を合成し、新しい反応場を与えることができる。このことは、枯渇金属種に頼らず、豊富な金属を用いて合成反応を実施することができることから、資源の有効利用に直結する。また、これらの触媒で達成さえた選択的反応は、従来法に比して、トータルのエネルギー効率がきわめて高く、効率的な合成反応として位置付けられる。社会全体がこのような反応を活用する方向を目指す端緒となる研究である。

Research Products

• [Journal Article] Catalytic Cycloisomerization of Conjugated Bisbutatrienes into Pentalene Skeletons: Synthesis and Properties of Bisbutatrienes with an Acenaphthene Backbone (2020)
  • Author(s): Konishi Akihito、Satake Shoya、Yasuda Makoto
  • Journal Title: Chemistry Letters Volume: 49 Issue: 5 Pages: 589-592
  • DOI: 10.1246/cl.200121
  • NAID: 130007840177
  • Peer Reviewed / Open Access
• [Journal Article] Carbometalation and Heterometalation of Carbon‐Carbon Multiple‐Bonds Using Group‐13 Heavy Metals: Carbogallation, Carboindation, Heterogallation, and Heteroindation (2020)
  • Author(s): Nishimoto Yoshihiro、Yasuda Makoto
  • Journal Title: Chemistry An Asian Journal Volume: 15 Issue: 6 Pages: 636-650
  • DOI: 10.1002/asia.201901730
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of (Z)‐β‐(Carbonylamino)alkenylindium through Regioselective anti‐Carboindation of Ynamides and Its Transformation to Multisubstituted Enamides (2020)
  • Author(s): Kang Kyoungmin、Sakamoto Kosuke、Nishimoto Yoshihiro、Yasuda Makoto
  • Journal Title: Chemistry A European Journal Volume: 26 Issue: 22 Pages: 4930-4934
  • DOI: 10.1002/chem.201905175
  • Peer Reviewed
• [Journal Article] Synthesis of α-Alkenyl α,β-Unsaturated Ketones via Dehydrogermylation of Oxagermacycles with Regeneration of the Germanium(II) Species (2019)
  • Author(s): Minami Yohei、Konishi Akihito、Yasuda Makoto
  • Journal Title: Organic Letters Volume: 21 Issue: 24 Pages: 9818-9823
  • DOI: 10.1021/acs.orglett.9b03454
  • Peer Reviewed
• [Journal Article] Synthesis of Cage-Shaped Aluminum Aryloxides: Efficient Lewis Acid Catalyst for Stereoselective Glycosylation Driven by Flexible Shift of Four- to Five-Coordination (2019)
  • Author(s): Tanaka Daiki、Kadonaga Yuichiro、Manabe Yoshiyuki、Fukase Koichi、Sasaya Shota、Maruyama Hikaru、Nishimura Sota、Yanagihara Mayu、Konishi Akihito、Yasuda Makoto
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 44 Pages: 17466-17471
  • DOI: 10.1021/jacs.9b08875
  • Peer Reviewed
• [Journal Article] Regioselective Synthesis of 5-Metalated 2-Pyrones by Intramolecular Oxymetalation of Carbonyl-ene-yne Compounds Using Indium Trihalide (2019)
  • Author(s): Yata Tetsuji、Kita Yuji、Nishimoto Yoshihiro、Yasuda Makoto
  • Journal Title: The Journal of Organic Chemistry Volume: 84 Issue: 21 Pages: 14330-14341
  • DOI: 10.1021/acs.joc.9b02186
  • Peer Reviewed
• [Journal Article] Regio- and Stereoselective Carboindation of Internal Alkynyl Ethers with Organosilicon or -stannane Nucleophiles (2019)
  • Author(s): Kang Kyoungmin、Nishimoto Yoshihiro、Yasuda Makoto
  • Journal Title: The Journal of Organic Chemistry Volume: 84 Issue: 21 Pages: 13345-13363
  • DOI: 10.1021/acs.joc.9b01505
  • Peer Reviewed
• [Journal Article] Geometrically Selective Synthesis of (E)-Enamides via Radical Allylation of Alkyl Halides with α-Aminoallylic Stannanes (2019)
  • Author(s): Suzuki Kensuke、Nishimoto Yoshihiro、Yasuda Makoto
  • Journal Title: Organic Letters Volume: 21 Issue: 17 Pages: 6589-6592
  • DOI: 10.1021/acs.orglett.9b01744
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Pheox- and Phebox-Aluminum Complexes: Application as Tunable Lewis Acid Catalysts in Organic Reactions (2019)
  • Author(s): Nishimoto Yoshihiro、Nakao Shuichi、Machinaka Shota、Hidaka Fumiko、Yasuda Makoto
  • Journal Title: Chemistry A European Journal Volume: 25 Issue: 46 Pages: 10792-10796
  • DOI: 10.1002/chem.201901791
  • Peer Reviewed
• [Journal Article] Open-Shell and Antiaromatic Character Induced by the Highly Symmetric Geometry of the Planar Heptalene Structure: Synthesis and Characterization of a Nonalternant Isomer of Bisanthene (2019)
  • Author(s): Konishi Akihito、Horii Koki、Shiomi Daisuke、Sato Kazunobu、Takui Takeji、Yasuda Makoto
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 26 Pages: 10165-10170
  • DOI: 10.1021/jacs.9b04080
  • Peer Reviewed
• [Journal Article] Enhancement of Antiaromatic Character via Additional Benzoannulation into Dibenzo[a,f]pentalene: Syntheses and Properties of Benzo[a]naphtho[2,1-f]pentalene and Dinaphtho[2,1-a,f]pentalene (2019)
  • Author(s): Akihito Konishi, Yui Okada, Ryohei Kishi, Masayoshi Nakano, Makoto Yasuda
  • Journal Title: J. Am. Chem. Soc. Volume: 141 Issue: 1 Pages: 560-571
  • DOI: 10.1021/jacs.8b11530
  • Peer Reviewed
• [Journal Article] Selective Oxymetalation of Terminal Alkynes via 6-Endo Cyclization: Mechanistic Investigation and Application to the Efficient Synthesis of 4-Substituted Isocoumarins (2018)
  • Author(s): Yuji Kita, Tetsuji Yata, Yoshihiro Nishimoto, Kouji Chiba, and Makoto Yasuda
  • Journal Title: Chem. Sci. Volume: 9 Issue: 28 Pages: 6041-6052
  • DOI: 10.1039/c8sc01537f
  • Peer Reviewed
• [Journal Article] Regio- and Stereoselective Allylindation of Alkynes Using InBr3 and Allylic Silanes: Synthesis, Characterization, and Application of 1,4-Dienylindiums toward Skipped Dienes (2018)
  • Author(s): Yoshihiro Nishimoto, Junyi Yi, Tatsuaki Takata, Akio Baba, and Makoto Yasuda
  • Journal Title: Molecules Volume: 23 Issue: 8 Pages: 1884-1897
  • DOI: 10.3390/molecules23081884
  • Peer Reviewed / Open Access
• [Journal Article] Stereocontrolled Synthesis of Triols Containing Four Asymmetric Centers: Application of C,O-Chelated Germyl Enolates to a Diastereoselective Aldol Reaction (2018)
  • Author(s): Yohei Minami, Akihito Konishi, Makoto Yasuda
  • Journal Title: Org. Lett. Volume: 20 Issue: 13 Pages: 4148-4152
  • DOI: 10.1021/acs.orglett.8b01778
  • Peer Reviewed
• [Journal Article] Regio- and Stereo-controlled Addition Reaction of Aminoallylic Stannanes to Aldehydes Mediated by Germanium Dichloride (2018)
  • Author(s): Kensuke Suzuki, Yoshihiro Nishimoto, Hiroshi Yunoki, Kensuke Tsuruwa, Naoto Esumi, and Makoto Yasuda
  • Journal Title: Chem. Lett. Volume: 47 Issue: 7 Pages: 821-824
  • DOI: 10.1246/cl.180291
  • NAID: 130007402813
  • Peer Reviewed
• [Journal Article] Construction of Polycyclic π‐Conjugated Systems Incorporating an Azulene Unit Following the Oxidation of 1,8‐Diphenyl‐9,10‐bis(phenylethynyl)phenanthrene (2018)
  • Author(s): Akihito Konishi, Atsushi Morinaga, Makoto Yasuda
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 34 Pages: 8548-8552
  • DOI: 10.1002/chem.201801915
  • Peer Reviewed
• [Journal Article] Anti-Carboalumination of Alkynes Using Aluminum Trihalide and Silyl Ketene Imines: Stereo- and Regioselective Synthesis of Alkenylaluminum Compounds Bearing a Cyano Group (2018)
  • Author(s): Yoshihiro Nishimoto, Rina Hirase, and Makoto Yasuda
  • Journal Title: Org. Lett. Volume: 20 Issue: 12 Pages: 3651-3655
  • DOI: 10.1021/acs.orglett.8b01371
  • Peer Reviewed
• [Journal Article] 1,8-Diphenyl-9,10-Bis(arylethynyl)phenanthrenes: Synthesis, Distorted Structure, and Optical Properties (2018)
  • Author(s): Konishi Akihito、Morinaga Atsushi、Fukuhara Gaku、Nishijima Masaki、Mori Tadashi、Kida Toshiyuki、Yasuda Makoto
  • Journal Title: Chemistry A European Journal Volume: 印刷中 Issue: 25 Pages: 6625-6631
  • DOI: 10.1002/chem.201800150
  • Peer Reviewed / Open Access
• [Journal Article] Indium Catalyzed Hydrofunctionalization of Styrene Derivatives Bearing a Hydroxy Group with Organosilicon Nucleophiles (2018)
  • Author(s): Yuji Kita, Tetsuji Yata, Yoshihiro Nishimoto, and Makoto Yasuda
  • Journal Title: J. Org. Chem. Volume: 83 Issue: 2 Pages: 740-753
  • DOI: 10.1021/acs.joc.7b02739
  • Peer Reviewed
• [Journal Article] Generation of α-Iminyl Radicals from α-Bromo Cyclic N-Sulfonylimines and Application to Coupling with Various Radical Acceptors Using a Photoredox Catalyst (2017)
  • Author(s): Esumi Naoto、Suzuki Kensuke、Nishimoto Yoshihiro、Yasuda Makoto
  • Journal Title: Chem. Eur. J. Volume: 24 Issue: 2 Pages: 312-316
  • DOI: 10.1002/chem.201704060
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Dibenzo[a,f]pentalene: Harmonization of the Antiaromatic and Singlet Biradical Character (2017)
  • Author(s): Akihito Konishi, Yui Okada, Motohiro Nakano, Kenji Sugisaki, Kazunobu Sato, Takeji Takui, and Makoto Yasuda
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 43 Pages: 15284-15287
  • DOI: 10.1021/jacs.7b05709
  • Peer Reviewed
• [Journal Article] Effect of Functional Groups in Organic Chlorides on Radical Reduction with Hydrostannane under Microwave Irradiation (2017)
  • Author(s): Yoshihiro Nishimoto, Satoshi Yazawa, Kensuke Kiyokawa, Takahito Kajiki, Yasunori Tsukahara, Tomohisa Yamauchi, Yuji Wada, Akio Baba, and Makoto Yasuda
  • Journal Title: Chem. Lett. Volume: 46 Issue: 8 Pages: 1116-1118
  • DOI: 10.1246/cl.170413
  • NAID: 130005907018
  • Peer Reviewed
• [Journal Article] Regio- and Stereoselective Anti-Carbozincation of Alkynyl Ethers Using ZnBr2 toward (Z)-β-Zincated Enol Ether Synthesis (2017)
  • Author(s): Nishimoto Yoshihiro、Kang Kyoungmin、Yasuda Makoto
  • Journal Title: Org. Lett. Volume: 19 Issue: 14 Pages: 3927-3930
  • DOI: 10.1021/acs.orglett.7b01847
  • Peer Reviewed
• [Journal Article] First anti-Selective Direct Michael Addition of α-Alkoxy Ketones to Enones by Cooperative Catalysis of Samarium(III) Trifluoromethanesulfonate and Tributyltin Methoxide (2017)
  • Author(s): Esumi Naoto、Nishimoto Yoshihiro、Yasuda Makoto
  • Journal Title: Eur. J. Org. Chem. Volume: 2017 Issue: 19 Pages: 2831-2835
  • DOI: 10.1002/ejoc.201700501
  • Peer Reviewed
• [Journal Article] Tuning Lewis Acidity by a Transannular pπ--σ* Interaction between Boron and Silicon/Germanium Atoms Supported by a Cage-Shaped Framework (2017)
  • Author(s): Akihito Konishi, Koichi Nakaoka, Hideto Nakajima, Kouji Chiba, Akio Baba, Makoto Yasuda
  • Journal Title: Chemistry - A European Journal Volume: 印刷中 Issue: 22 Pages: 5219-5223
  • DOI: 10.1002/chem.201700659
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] C3-Symmetric Boron Lewis Acid with a Cage-Shape for Chiral Molecular Recognition and Asymmetric Catalysis (2017)
  • Author(s): Akihito Konishi, Koichi Nakaoka, Hikaru Maruyama, Hideto Nakajima, Tomohiro Eguchi, Akio Baba, and Makoto Yasuda
  • Journal Title: Chem. Eur. J. Volume: 23 Issue: 6 Pages: 1273-1277
  • DOI: 10.1002/chem.201605712
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Characterization of Sterically Crowded Aryloxides: 'Mitsubishi'-Class of Tetrametallic Aluminum Complexes (2017)
  • Author(s): Akihito Konishi, Hideto Nakajima, Hikaru Maruyama, Sachiko Yoshioka, Akio Baba, and Makoto Yasuda
  • Journal Title: Polyhedron Volume: 125 Pages: 130-134
  • DOI: 10.1016/j.poly.2016.10.019
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Coupling Reaction of Enol Derivatives with Silyl Ketene Acetals Catalyzed by Gallium Trihalides (2016)
  • Author(s): Yoshihiro Nishimoto, Yuji Kita, Hiroki Ueda, Hiroto Imaoka, Kouji Chiba, Makoto Yasuda, and Akio Baba
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 33 Pages: 11837-11845
  • DOI: 10.1002/chem.201602150
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] First Isolation and Characterization of the Highly Coordinated Group 14 Enolates; Effects of the Coordination Controls on the Geometry and Tautomerization of Germyl Enolates (2016)
  • Author(s): Akihito Konishi, Yohei Mimani, Takahisa Hosoi, Kouji Chiba, and Makoto Yasuda
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 36 Pages: 12688-12691
  • DOI: 10.1002/chem.201603147
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of Thioethers by InI3-Catalyzed Substitution of Siloxy Group Using Thiosilanes (2016)
  • Author(s): Yoshihiro Nishimoto, Aya Okita, Akio Baba, Makoto Yasuda
  • Journal Title: Molecules Volume: 21 Issue: 10 Pages: 1330-1336
  • DOI: 10.3390/molecules21101330
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis of 1,4-Dicarbonyl Compounds from Silyl Enol Ethers and Bromocarbonyls, Catalyzed by an Organic Dye under Visible Light Irradiation with Perfect Selectivity for the Halide Moiety over the Carbonyl Group (2016)
  • Author(s): Naoto Esumi, Kensuke Suzuki, Yoshihiro Nishimoto, and Makoto Yasuda
  • Journal Title: Org. Lett. Volume: 18 Issue: 21 Pages: 5704-5707
  • DOI: 10.1021/acs.orglett.6b02869
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Photoredox α-Allylation of α-Halocarbonyls with Allylboron Compounds Accelerated by Fluoride Salts under Visible Light Irradiation (2016)
  • Author(s): Itaru Suzuki, Naoto Esumi, and Makoto Yasuda
  • Journal Title: Asian J. Org. Chem. Volume: 5 Issue: 2 Pages: 179-182
  • DOI: 10.1002/ajoc.201500475
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Characterization, and Properties of a Benzofuran-based Cage-shaped Borate: Photo Activation of Lewis Acid Catalysts (2016)
  • Author(s): Akihito Konishi, Ryosuke Yasunaga, Kouji Chiba, and Makoto Yasuda
  • Journal Title: Chem. Commun. Volume: 52 Issue: 16 Pages: 3348-3351
  • DOI: 10.1039/c6cc00291a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Indium Tribromide Catalyzed Coupling Reaction of Enol Ethers with Silyl Ketene Imines toward Synthesis of ß,γ-Unsaturated Nitriles (2015)
  • Author(s): Yoshihiro Nishimoto, Takashi Nishimura, Makoto Yasuda
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 50 Pages: 18301-18308
  • DOI: 10.1002/chem.201503414
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Cage-shaped Aluminum Aryloxides as a Lewis Acid Catalyst (2019)
  • Author(s): Makoto Yasuda
  • Organizer: The 1st Symposium for the Distinguished Lectureship Awards on The International Cutting-Edge Organic Chemistry in Asia
  • Int'l Joint Research / Invited
• [Presentation] Germyl EnolatesCharacterizations, Structures and Reactivity of Stereoselective Aldol Reactions (2019)
  • Author(s): Makoto Yasuda
  • Organizer: International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-16)
  • Int'l Joint Research / Invited
• [Presentation] Cage-Shaped Aluminum Lewis Acid Catalyst for Selective Reactions (2019)
  • Author(s): Makoto Yasuda
  • Organizer: The 18th Asian Chemical Congress and the 20th General AssembIy of the Federation of Asian Chemical Socieities (ACC 2019)-Joint FACS/IUPAC ChemRAWN Symposium on Green Catalysis
  • Int'l Joint Research / Invited
• [Presentation] Regio- and Stereoselective Synthesis of Functionalized Organic Compounds via Main Group Organometallic Compounds (2018)
  • Author(s): Makoto Yasuda
  • Organizer: The University of Hong Kong -Osaka University, 2nd Joint Symposium on Materials Research - Diverse Aspects of Future Chemistry -
  • Int'l Joint Research / Invited
• [Presentation] 典型金属の性状制御 (2018)
  • Author(s): 安田 誠
  • Organizer: 第５回 新学術領域研究「反応集積化が導く中分子戦略：高次生物機能分子の創製」若手シンポジウム
  • Invited
• [Presentation] Lewis Acidity of Borates Controlled by Their Cage-Structure (2018)
  • Author(s): Makoto Yasuda
  • Organizer: Strasbourg University -Osaka University, Joint Symposium on “Diverse Facets of Chemistry II”
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of Isocoumarins by Intramolecular Oxyindation of Alkynes (2017)
  • Author(s): 喜多悠二, 西本能弘, 安田 誠
  • Organizer: ISPAC 2017
  • Int'l Joint Research
• [Presentation] Change of Cyclization Mode by Indium to Synthesize Isocoumarins (2017)
  • Author(s): Makoto Yasuda
  • Organizer: The 12th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-12)
  • Int'l Joint Research / Invited
• [Presentation] Boron or Aluminum in Cage-shaped Organic Ligands for Tunable Catalysts (2016)
  • Author(s): Makoto Yasuda
  • Organizer: International Symposium on Pure & Applied Chemistry (ISPAC) 2016
  • Place of Presentation: Kuching, Sarawak, Malaysia
  • Year and Date: 2016-08-15
  • Int'l Joint Research / Invited
• [Presentation] Benzofuran-based Cage-shaped Borates for a Lewis Acid Catalyst and its Activation by Photo Irradiation (2016)
  • Author(s): Akihito Konishi, Ryosuke Yasunaga, Kouji Chiba, Makoto Yasuda
  • Organizer: The 12th International Symposium on Organic Reactions (ISOR-12)
  • Place of Presentation: Kyoto, Japan
  • Year and Date: 2016-04-22
  • Int'l Joint Research / Invited
• [Presentation] 金属と炭素の協同作用：芳香族化合物を選択的に見分ける金属触媒の設計 (2015)
  • Author(s): 安田 誠
  • Organizer: 平成27年度有機合成化学北陸セミナー
  • Place of Presentation: 富山観光ホテル
  • Year and Date: 2015-10-02
  • Invited
• [Presentation] Lewis Acids Bearing Cage-Shaped Organic Ligands for Catalysts of Selective Reactions (2015)
  • Author(s): Makoto Yasuda
  • Organizer: Golden Jubilee Chemistry Conference
  • Place of Presentation: NUSS Kent Ridge Guild House, Singapore
  • Year and Date: 2015-08-06
  • Int'l Joint Research / Invited
• [Presentation] 有機骨格による金属錯体設計と触媒利用 (2015)
  • Author(s): 安田 誠
  • Organizer: 第50回有機反応若手の会
  • Place of Presentation: 広島エアポートホテル／フォレストヒルズガーデン
  • Year and Date: 2015-07-29
  • Invited