Highly Enantioselective Construction of Spiro[4H-pyran …

Cycloaddition for the Synthesis of Spiro[4-cyclohexanone-1,3′-oxindoline] ..
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Highly Enantioselective Construction of Spiro ..

of Sci.) ODO, Toshifumi; KUTSUMURA, Noriki; SAITO, Takao
4F2-11 Withdrawn
4F2-12 Catalytic trifluoromethylation of indole derivatives (ERATO-JST / RIKEN) MIYAZAKI, Ayako; SHIMIZU, Ryo; EGAMI, Hiromichi; SODEOKA, Mikiko
4F2-13 The Development of Iron-catalyzed Synthesis of Heterocyclic Compounds (Tottori University) SAKAE, Mikei; OSHITANI, Shunsuke; HAYASE, Shuichi; NOKAMI, Toshiki; KAWATSURA, Motoki; ITOH, Toshiyuki

Chair: NOKAMI, Toshiki (11:20-12:20)
* 11:10-11:20: interval for laptop PC connection.(4F2-15, 4F2-16, 4F2-17, 4F2-18, 4F2-19, 4F2-20)4F2-15 Efficient Synthesis of Indole Alkaloids via Electrophilic Allylation Promoted by Pd-catalyst (Nagasaki Univ.) KURODA, Azusa; ONODERA, Gen; KIMURA, Masanari
4F2-16 Synthesis of Nitrogen-Containing Heterocycles via Amphiphilic Allylation of Imines and Nitriles (Nagasaki Univ.) YAMADA, Naoshi; SANADA, Syohei; ONODERA, Gen; KIMURA, Masanari
4F2-17 Development of a Synthetic Method for Chiral 3-Spiro--methylene--butyrolactone Oxindoles via Enantioselectively Catalytic Amido-allylation of Isatin Derivatives (Faculty of Engineering, Shizuoka University) MURATA, Yusuke; ISHIDA, Masahiro; SENGOKU, Tetsuya; TAKAHASHI, Masaki; YODA, Hidemi
4F2-18 Synthetic Studies toward Stemaphylline, a New Insecticidal Stemona Alkaloid (Faculty of Engineering, Shizuoka University) SENGOKU, Tetsuya; MAKINO, Yuto; ISOZAKI, Yuya; TAKAHASHI, Masaki; YODA, Hidemi
4F2-19 Stereoselective Synthesis of (+)-Batzellaside B from L-Pyroglutamic Acid (Faculty of Engineering, Shizuoka University) WIERZEJSKA, Jolanta; SUZUKI, Chihiro; SENGOKU, Tetsuya; TAKAHASHI, Masaki; YODA, Hidemi
4F2-20 Synthesis of Indolizines from Ethynlpyridines and their Oligomerization (Kochi Univ.

Organocatalytic Synthesis of Spiro[pyrrolidin-3,3′-oxindoles] with High Enantiopurity and Structural Diversity
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Through a Domino Knoevenagel/Michael/Cyclization Sequence ..

(Nagoya Institute of Technology) HAYASHI, Masashi; SANO, Masahide; NAKAMURA, Shuichi

Chair: MASE, Nobuyuki (16:30-17:20)
* 16:20-16:30: interval for laptop PC connection.(2E5-46, 2E5-48, 2E5-49, 2E5-50)2E5-46* Total Synthesis of Prostaglandin E1 Methyl Ester by Three Pots Sequences (Graduate School of Science, Tohoku University) UMEMIYA, Shigenobu; HAYASHI, Yujiro
2E5-48 Development of Novel Chiral P3 Phosphazene Superbase Catalyst (Graduate School of Science, Tohoku Univ.) GOTO, Kengo; TERADA, Masahiro
2E5-49 Development of Novel Herically Chiral Spiro P3 Phosphazene Superbase Catalyst (Graduate School of Science, Tohoku Univ.) OISHI, Masafumi; GOTO, Kengo; TERADA, Masahiro
2E5-50 Development of New Optically Active Guanidinophosphazene Organo Super Base Catalyst and Its Application to Catalytic Asymmetric Reactions (Graduate School of Science, Tohoku Univ.; Daiichi Sankyo Co., LTD.) TAKEDA, Tadahiro; TERADA, Masahiro
Chair: NAKATA, Kenya (09:50-10:50)
* 9:40-9:50: interval for laptop PC connection.(3E5-06, 3E5-07, 3E5-08, 3E5-09, 3E5-10, 3E5-11)3E5-06 Development of Highly Enantioselective Cyano-Ethoxycarbonylation of Isatin Derivatives (Nagoya Univ.; Okayama Univ.; CREST) OGURA, Yoshihiro; SAKAKURA, Akira; ISHIHARA, Kazuaki
3E5-07 Synthesis of Chiral Binaphthyl Pyrophosphate and Development to Chiral Broensted Acid Catalysts (Nagoya Univ.; Okayama Univ.; CREST) OKAMOTO, Haruka; NAKATSUJI, Hidefumi; SAKAKURA, Akira; ISHIHARA, Kazuaki
3E5-08 Enantioselective Diels-Alder Reaction of 1,2-Dihydropyridines with -Heterosubstituted Acroleins Catalyzed by Chiral Primary Ammonium Salts.

Highly Enantioselective Synthesis of Spiro[cyclohexanone-oxindoles] and Spiro[cyclohexanone-pyrazolones] by Asymmetric Cascade [5+1] …
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Proline catalysis has also been used for reaction with highly activated ketone electrophiles 48 (). The self condensation of 2,2-dimethyl-1,3-diox-5-one was observed by Enders and Grondal, producing adduct 49a in 94% ee. Zhang an coworkers reported the use of α-trifluoromethyl ketones for the synthesis of aldol adducts such as 49b with only 10 mol% proline with excellent yields, though the best ee observed was 64%. Maruoka demonstrated the feasibility of using α-keto esters as electrophiles with cyclohexanone as donor in 2005. Aldol adduct 49c was obtained in excellent enantio- and diastereoselectivity, although 50 mol% catalyst was needed to achieve these excellent results. Adduct 49c was taken on to complete the synthesis of a key intermediate for the synthesis of (S)-oxybutynin 50. The research groups of Zhang and Shao reported the use of α-keto esters as electrophiles for the acetone aldol catalyzed by proline in 2006 using 60 and 50 mol% proline, respectively., α-Keto phosphonates have also been used as substrates for the proline-catalyzed acetone aldol, yielding the desired aldol adducts 49 in high yield and enantioselectivity when electron-deficient aldehydes are employed as the acceptors, using a catalyst loading of 20 mol%. Electron-rich aromatic substrates, however, gave lower yields due to their lower reactivity. Adduct 49g was obtained in only 32% yield using 50 mol% proline.

Full Paper Highly Enantioselective Synthesis of Spiro[cyclohexanone-oxindoles] and Spiro[cyclohexanone-pyrazolones] by Asymmetric Cascade [5+1] …
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The Catalytic Asymmetric Fischer Indolization

An enantioselective organocatalytic approach to the rapid synthesis of spiro[pyrrolidin-3,3′-oxindole] derivatives with high enantiopurity and structural diversity is described.

The first catalytic asymmetric Fischer indolization is reported

When proline was used with 2-butanone 167 and para-nitrobenzaldehyde 74, the linear adduct 42h was obtained in 65% yield and 77% ee (). Many catalysts have been applied to this reaction enhancing both the yield and selectivity of the linear adduct 42h, but also provided access to both diastereomers of the branched adduct 168 (). The linear product was favored by catalysts 88,90,99,94,107,103,108,, 148,117, and 128. Among these catalysts, Nájera’s binaphthyl amine 108 provided the linear adduct 42h with the best yield and selectivity. Xiao’s cyclohexanediamine catalyst 112, on the other hand, gave the branched product 168 with excellent selectivity for the anti diastereomer, though with only moderate selectivity for the branched product over the linear. The enantioselectivity for catalyst 112 was also high. Trinitroanilide catalyst 116 also favors the anti adduct, but the reaction conditions are less appealing, as HMPA is used as solvent. Thiourea catalyst 152 also provide the anti adduct in good selectivity. Luo and Cheng’s cyclohexanediamine catalyst 125 gave the syn adduct in excellent selectivity and yield. With these developments, each aldol adduct isomer can be synthesized with good selectivity.