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Shimizu, Yohei; Shi, Shi-Liang; Usuda, Hiroyuki; Kanai, Motomu; Shibasaki, Masakatsu. Catalytic Asymmetric Total Synthesis of ent-Hyperforin. Angewandte.

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Presentation on theme: "Shimizu, Yohei; Shi, Shi-Liang; Usuda, Hiroyuki; Kanai, Motomu; Shibasaki, Masakatsu. Catalytic Asymmetric Total Synthesis of ent-Hyperforin. Angewandte."— Presentation transcript:

1 Shimizu, Yohei; Shi, Shi-Liang; Usuda, Hiroyuki; Kanai, Motomu; Shibasaki, Masakatsu. Catalytic Asymmetric Total Synthesis of ent-Hyperforin. Angewandte Chemie, International Edition (2010), 49(6), , S1103/1-S1103/75.

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4 Chiral bisoxazolidinone ligands
(BOX ligands)

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6 Diels Alder Reaction The Diels Alder Reaction constitutes a very powerful method for the generation of a six membered ring.

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9 A wide variety of dienes and dienophiles are possible
A wide variety of dienes and dienophiles are possible. Most commonly, the dienophile possesses an electron withdrawing group, as shown in the examples below.

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13 MOM ethers as protecting groups for alcohols
MOM = Methoxymethyl

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25 LDA = lithium diisopropylamide,
Diisopropylamine pKa = 36 HMPA = hexamethylphosporamide A polar solvent

26 Isoprene

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34 The Claisen Rearrangement
Like the Cope Rearrangement, this is an electrocyclic process, categorized as a 3,3-sigmatropic rearrangement

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37 Hydroboration-oxidation sequence accomplishes anti-Markovnikov addition of water to the carbon-carbon double bond Link

38 Disiamylborane is a very hindered organoborane, with high selectivity for the terminal position of a terminal double bond.

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42 CSA = camphorsulfonic acid, pKa = 1.2

43 Markovnikov’s Rule

44 The regioselectivity of the Markovnikov Rule is caused, mechanistically, by the tendency to form the more stable carbocation, during the initial electrophilic addition to the double bond, as shown above.

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47 The Swern Oxidation

48 Mechanism of the Swern Oxidation

49 Reagents which result in an ‘activated’ form of DMSO

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51 Hoveyda-Grubbs 2nd generation catalyst =

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