The nucleophilic addition of alpha-metallated 1,3-dioxanes to planar chiral cationic eta3-allylmolybdenum complexes. Synthesis of (2E,5S,6R,7E)-6-methyl-8-phenylocta-2,7-dienoic acid methyl ester, a key component of the Cryptophycins.
Two adjacent stereogenic centres and a pendant alkene were constructed via nucleophilic addition of a 1,3-dioxan-4-ylcopper(I) reagent to a cationic eta3-allylmolybdenum complex as part of a synthesis of (2E,5S,6R,7E)-6-methyl-8-phenylocta-2,7-dienoic acid, a key component of the Cryptophycins. Oxidative addition of Mo(CO)(4)(THF)(2) to allyl benzoates provides an efficient synthesis of eta3-allylmolybdenum(dicarbonyl) complexes.
Cooksey
John
J
Department of Chemistry, Leeds University, Leeds, LS2 9JT, UK.
Gunn
Andrew
A
Kocienski
Philip J
PJ
Kuhl
Alexander
A
Uppal
Sukhjinder
S
Christopher
John A
JA
Bell
Richard
R
D000498:Allyl Compounds / Q000737:chemistry; D000970:Antineoplastic Agents / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D047630:Depsipeptides; D004146:Dioxanes / Q000737:chemistry*; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010456:Peptides, Cyclic / Q000737:chemistry*; D013237:Stereoisomerism
D000498:Allyl Compounds; D000970:Antineoplastic Agents; D002412:Cations; D047630:Depsipeptides; D004146:Dioxanes; D004952:Esters; D009942:Organometallic Compounds; D010456:Peptides, Cyclic; C088419:cryptophycin; D003300:Copper; D008982:Molybdenum