Organocopper Reagents

Lipshutz, Bruce H.

doi:10.1016/b978-0-08-052349-1.00004-4

Cited by 27 publications

(5 citation statements)

References 140 publications

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“…The first step in our synthetic approach to the (-)salicylihalamides starting from alcohol 7 was its conversion to bromide 9 (Scheme 2). 10 Subsequent reaction with a higher order allylcuprate 11 gave rise to allylated compound 10 with overall retention of stereochemistry at C12 in the two-step process. Hydrolysis of acetonide 10 with 70% acetic acid provided lactol 11, which was oxidized selectively to lactone 12.…”

Section: Resultsmentioning

confidence: 99%

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Formal Total Syntheses of the (−)-Salicylihalamides A and B From d-Glucose and l-Rhamnose

Haack

Diederich

et al. 2005

J. Org. Chem.

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[reaction: see text] Two formal total syntheses of the (-)-salicylihalamides, based on chiral pool approaches, are reported. D-glucose and L-rhamnose were used to prepare advanced intermediates 23 and 54, which can be converted in three or four steps, respectively, to the target compounds. The synthesis of 23 from a known D-glucose-derivative was accomplished in 12 steps and 17% overall yield, and the synthesis of 54 from a known L-rhamnose-derivative was done in nine steps and 6% overall yield. A key step in the synthesis was a ring-closing metathesis reaction to prepare the macrocyclic ring system. It was demonstrated that the phenolic protecting group was critical for inducing the preferential formation of the desired E isomer. It was further shown that the protecting group at the C13 hydroxyl group had no significant influence on the E:Z ratio during the ring-closing metathesis reaction.

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Section: Resultsmentioning

confidence: 99%

“…)-1-Methylbut-3-enyl)(3R,5S)oxolane-2,3-diol (11). A solution of 10 (2.57 g, 12.1 mmol) in 70% aqueous acetic acid was stirred at 70 °C for 3 h. The reaction mixture was concentrated in vacuo and subsequently extracted with chloroform.…”

Section: -((1smentioning

confidence: 99%

Formal Total Syntheses of the (−)-Salicylihalamides A and B From d-Glucose and l-Rhamnose

Haack

Diederich

et al. 2005

J. Org. Chem.

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“…The acrylonitrile substructure itself holds promise for a separate subsequent chemistry. To be mentioned in this respect are transformations to aldehydes, conjugate cuprate additions, , hydrogenolysis, hydrolysis, hydrazinolysis, cycloadditions, and the like.…”

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confidence: 99%

Novel Class of Morphinans with Acrylonitrile Incorporated Substructures as Key Intermediates for Non-Oxygen-Bridged Opioid Ligands

et al. 2001

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“…[51][52][53] The secondary hydroxyl group of 9 was converted to its corresponding triflate and used immediately, without purification, in the next step. Reaction of the triflate with a higher order allylcyanocuprate 54 provided allylated intermediate 10 with complete inversion of stereochemistry in 84% yield. Initial attempts to achieve this conversion employing the mesylate, tosylate, or imidazolate of alcohol 9 were unsuccessful.…”

Section: Resultsmentioning

confidence: 99%

Formal Total Synthesis of (+)-Salicylihalamides A and B: A Combined Chiral Pool and RCM Strategy

et al. 2003

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The formal total synthesis of the (+)-salicylihalamides A and B is detailed, utilizing a chiral pool approach to generate the three stereogenic centers and a ring-closing metathesis (RCM) for the formation of the macrocyclic ring structure. Starting from a known glucose-derived alcohol, the formal total synthesis was achieved in an efficient 13-step protocol in 26% overall yield. It was found that substitution at the remote phenolic group significantly influenced the ratio of the E- and Z-double bond products in the RCM step. The introduction of phenol protecting groups provided E-isomers preferentially and also enhanced the rates of the RCM reactions.

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Organocopper Reagents

Cited by 27 publications

References 140 publications

Formal Total Syntheses of the (−)-Salicylihalamides A and B From d-Glucose and l-Rhamnose

Formal Total Syntheses of the (−)-Salicylihalamides A and B From d-Glucose and l-Rhamnose

Novel Class of Morphinans with Acrylonitrile Incorporated Substructures as Key Intermediates for Non-Oxygen-Bridged Opioid Ligands

Formal Total Synthesis of (+)-Salicylihalamides A and B: A Combined Chiral Pool and RCM Strategy

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