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Published byLynn Jenkins Modified over 7 years ago
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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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Chiral bisoxazolidinone ligands
(BOX ligands)
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Diels Alder Reaction The Diels Alder Reaction constitutes a very powerful method for the generation of a six membered ring.
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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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MOM ethers as protecting groups for alcohols
MOM = Methoxymethyl
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LDA = lithium diisopropylamide,
Diisopropylamine pKa = 36 HMPA = hexamethylphosporamide A polar solvent
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Isoprene
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The Claisen Rearrangement
Like the Cope Rearrangement, this is an electrocyclic process, categorized as a 3,3-sigmatropic rearrangement
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Hydroboration-oxidation sequence accomplishes anti-Markovnikov addition of water to the carbon-carbon double bond Link
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Disiamylborane is a very hindered organoborane, with high selectivity for the terminal position of a terminal double bond.
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CSA = camphorsulfonic acid, pKa = 1.2
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Markovnikov’s Rule
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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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The Swern Oxidation
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Mechanism of the Swern Oxidation
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Reagents which result in an ‘activated’ form of DMSO
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Hoveyda-Grubbs 2nd generation catalyst =
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