Cuprates, conjugate addition

Cuprate conjugate additions. One step in a recent synthesis of (-t-)-modhephene (3). a natural sesquiterpene with a (3.3.3)propellane skeleton, involved conjugate addition of lithium dimethylcuprate to 1. The desired reaction proved difficult... 

Cuprate conjugate addition to a, j6-unsaturated carbonyl compounds involves an initial 7r-complexation of the a, fi-unsaturated double or triple bond by copper followed by an oxidative addition (see Oxidative Addition) resulting in a... 

Similar chemistry using chiral sultam auxiliaries demonstrates superior yields and selectivities for specific cases of cuprate conjugate additions, but have not yet been extended to the more complex multistep transformation series illustrated above. Moderate selectivities have been obtained in alkyl cuprate additions to y-aminocrotonate equivalents where the nitrogen is derived from the oxazolidinone. ... 

Scheme 3.35. Tetrahydrofurar synthesis by means of MOM a-alkoxy alkyl cuprate conjugate additions followed by Lewis acid-promoted cyclization (MOM = methoxymethyl) [129].

R583 S. Woodward, Decoding the Black Box Reactivity that is Organo-cuprate Conjugate Addition Chemistry , Chem. Soc. Rev., 2000, 29, 393... 

Hong CY, Kado N, Overman LE (1993) Asymmetric-synthesis of either enantiomer of opium-alkaloids and morphinans - total synthesis of (—)-dihydrocodeinone and (-1-)-dihydrocodeinone and (—)-morphine and (+)-morphine. J Am Chem Soc 115 11028-11029 Mulzer J, Dumer G, Trauner D (1996) Formal total synthesis of (—)-morphine by cuprate conjugate addition. Angew Chem hit Ed 35 2830-2832... 

The lithio cuprate conjugate-addition procedure for the preparation of 1-PGEi methyl ester has been studied in considerable detail by Sih, who introduced this useful process to prostaglandin synthesis (3T). 

Nakamura, E., Yamanaka, M., Mori, S. 2000. Complexation of Lewis acid with trialkylcopper (III) On the origin of BF3-Acceleration of cuprate conjugate addition. J. Am. Chem. Soc. 122 1826-1827. 

Mulzer, J. Durner, G. Trauner, D. "Formal Total Synthesis of (-)-Morphine by Cuprate Conjugate Addition" Angew. Chem. Int. Ed. 1996, 35, 2830-2832. 

Clive et al. designed a synthesis of both otteliones A (135) and B (136), featuring an efHcient cuprate conjugate addition/Grignard reaction/RCM sequence... 

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