Asymmetric 1,4-additions of coordinated MeCu.BF3 to chiral enoates: enantioselective syntheses of (S)-(−)-citronellic acid

Oppolzer, Wolfgang; Moretti, Robert; Godal, Thierry; Meunier, Annge; Löher, Heinz

doi:10.1016/s0040-4039(01)99824-7

Cited by 67 publications

(12 citation statements)

References 22 publications

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“…The asymmetric synthesis of (S)-citronellic acid was achieved using this method in 92% ee (eq 4). 9 Similar results were obtained with a dicyclohexylsulfonamide chiral auxiliary, providing the methyl addition product in >94% ee (eq 5). 10 Displacement Reactions.…”

Section: Introductionsupporting

confidence: 66%

Methylcopper-Tributylphosphine

Linderman¹

2001

Encyclopedia of Reagents for Organic Synthesis

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Section: Introductionsupporting

confidence: 66%

Methylcopper-Tributylphosphine

Linderman¹

2001

Encyclopedia of Reagents for Organic Synthesis

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“…to other reactions such as asymmetric 1,6additions [3b] [25], ene processes [26], and enolate functionalizations [ 131.…”

Section: Preparation Of Enantiomerically Pure (-)-mentioning

confidence: 99%

Asymmetric Diels‐Alder Reactions of Neopentyl‐Ether‐Shielded Acrylates and Allenic Esters: Syntheses of (−)‐Norbornenone and (−)‐β‐Santalene

Oppolzer

Chapuis

Dupuis

et al. 1985

Helvetica Chimica Acta

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Starting from (+)-or (-)-camphor, the antipodal alcohols 14 and 18, respectively, have been prepared; the corresponding acrylates 15 and 19 underwent TiCl,(i-PrO)2-mediated Diel.vAlder additions to cyclopentadiene to give adducts 20a and 22a respectively, with 95% endo-and 99.2% n-face selectivities. Adduct 22a was converted to enantiomerically pure norbornenone 26. Addition of 1,3-butadiene to acrylate 15 in the presence of TiC1, Introduction. ~ Given the fundamental role of the Diels-Alder reaction in organic synthesis [I], it is without question that the control of its absolute topicity constitutes a topic of pressing importance. It was, however, not until recently that substantial effort has been devoted to and hence significant progress achieved in this area [2].As an extension of a preliminary communication [3], we report here in detail the first successful surmounting of the threshold of 99 % face-stereodifferentiation in the Diels-Alder process. Its value is illustrated by application to the syntheses of enantiomerically pure building blocks and also of a natural product. The starting point for this work was the encouraging chiral induction observed with Lewis-acid-promoted ene-type cyclizations (1h2) [4] and [4+2] cycloadditions (3-4) [5] of 8-phenylmenthyl enoates

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“…BF, .n-Bu,P-complex to chiral crotonate 64 followed by saponification (equation 737) 1626. Appendix to 'The synthesis of carboxylic acids and esters' 285 to acids with the opposite configuration from 63, but with lower ee values An enantioselective synthesis of (S)-( -)-citronellic acid (65) in 92 percent optical purity has been accomplished via addition of 4-methyl-3-pentenylcopper.…”

Section: *9 Michael Reactions and Related Conjugate Additionsmentioning

confidence: 99%