Regio- and Stereocontrolled Synthesis of Terminal 1,3,5-Triene Monoxides via Diene-Iron Tricarbonyl Complexes

Franck‐Neumann, M.; Abdali, Abdelkrim; Colson, Pierre-Jean; Sedrati, M.

doi:10.1055/s-1991-34722

Cited by 10 publications

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“…The only other oxidative method known in literature is the Sharpless epoxidation of allylic and homoallylic alcohols with an iron tricarbonyl-protected dienic functionality. The base-catalyzed dehydrochlorination of chlorohydrins serves as an nonoxidative method for the indirect epoxidation of iron tricarbonyl complexes with unfunctionalized double bonds.…”

Section: Resultsmentioning

confidence: 99%

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Iron Tricarbonyl Complexes in Oxidation Chemistry: Regio- and Stereoselective Oxyfunctionalization of Trienes by Singlet Oxygen and Dimethyldioxirane

Adam

Schuhmann

1996

J. Org. Chem.

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The versatility of the iron tricarbonyl fragment as protecting group in the oxyfunctionalization of trienes has been examined. The photooxygenation of the unsaturated iron complexes 1−3 at low temperatures (−80 °C) afforded after Ph3P reduction the allylic alcohols 4, 4‘, 13, and 22 in good to excellent yields. The persistence of the intermediary allylic hydroperoxides is reflected in the distance between the iron fragment and the reacting free double bond. Only the hydroperoxides derived from the homoallylic (most distant) substrate 1 are persistent enough to undergo the titanium tetraisopropoxide-catalyzed oxygen transfer to β-hydroxy epoxides. Epoxidation of the complexes 1 and 2a with dimethyldioxirane could be optimized in boiling acetone to suppress oxidative destruction of the iron tricarbonyl ligand. The deprotection of the organic ligand with cerium(IV) ammonium nitrate (CAN) enables the convenient preparation of multiply functionalized cyclohexadienes. In contrast to these regio- and stereoselectively controlled transformations, the corresponding unprotected trienes 10 and 19a react with singlet oxygen and dioxirane at all double bonds without any particular preference.

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Section: Resultsmentioning

confidence: 99%

“…The iron tricarbonyl complexes 1 and 2a and their oxyfunctionalized derivatives (Scheme and 3) were conveniently decomplexed with cerium(IV) ammonium nitrate , (CAN) mostly in high yields (up to 98%). Best results were obtained at a reaction time of one day under an argon gas atmosphere and 3 equiv of CAN at −5 °C.…”

Section: Resultsmentioning

confidence: 99%

Iron Tricarbonyl Complexes in Oxidation Chemistry: Regio- and Stereoselective Oxyfunctionalization of Trienes by Singlet Oxygen and Dimethyldioxirane

Adam

Schuhmann

1996

J. Org. Chem.

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“…In contrast, alkylation of (dienone)Fe(CO) 3 complexes 45 at the carbon β to the diene, or halogenation of the silyl enol ether derived from 45, proceeds with minimal selectivity (eqn. 15) [35,36]. In all of these cases the diastereoselectivity has been shown to be the result of kinetic control.…”

Section: S-trans S-cismentioning

confidence: 96%

Stoichiometric Applications of Acyclic π-Organoiron Complexes to Organic Synthesis

Donaldson¹

2000

COC

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Abstract:The application of acyclic (diene)iron complexes and (pentadienyl)iron cations in organic synthesis has steadily increased over the past 20 years. This is due to their ease of preparation, their stability toward a wide variety of reaction conditions, the manifold method for removal of the Fe(CO) 3 group, and the low cost of iron carbonyls. The (tricarbonyl)iron adjunct may serve in three capacities: i) as a protecting group for conjugated dienes, ii) to direct the formation of chiral centers adjacent to the complexed dient, and iii) to stabilize the formation of positive charge adjacent ot the complexed diene (i.e. pentadienyl cations). Specific examples of these attributes will be presented in this review. One of the advantages of stoichiometric organometallic reagents is the ability to repeatedly utilize the same metal center to control a number of different bond forming reactions. Six examples will be presented which demonstrate this potential for acyclic (diene)iron complexes and (pentadienyl) iron cations.

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Highly Stereoselective Total Synthesis of Multiply Protected 3-Amino-3,6-dideoxyaldohexoses (Mycosamine/Mycaminose) by Aldol Condensation Reaction, Mediated by Tin Triflate, of Tricarbonyliron/α-Aminodienone Complexes

2000

Self Cite

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The divalent tin enol ether of the racemic complex between N‐BOC‐α‐aminoheptadienone and tricarbonyliron reacts with both enantiomers of protected lactaldehydes to yield predominantly one optically active, easily isolable ketol diastereoisomer (45%). From the enantiomerically pure (S)‐(+) complex and (R)‐(+)‐tert‐butyldimethylsilyloxylactaldehyde, the major ketol is obtained almost exclusively (isolated yield 86%). From there, the multiply protected 3‐amino‐3,6‐dideoxy‐D‐aldohexose mycosamine is obtained in a few high‐yield steps (decomplexation, stereospecific reduction to an anti‐1,3‐diol, transformation into a diacetate and ozonolysis; absolute configurations S,S,S,R). Reduction of the ketol before decomplexation completely reverses the stereochemistry of the reaction [control by the Fe(CO)3 and not by the hydroxy group → syn‐diol], also giving access to the (R,S,S,R) series (configuration of the N,N‐dimethylated mycaminose). The key structures were determined by X‐ray diffraction.

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Regio- and Stereocontrolled Synthesis of Terminal 1,3,5-Triene Monoxides via Diene-Iron Tricarbonyl Complexes

Cited by 10 publications

References 0 publications

Iron Tricarbonyl Complexes in Oxidation Chemistry: Regio- and Stereoselective Oxyfunctionalization of Trienes by Singlet Oxygen and Dimethyldioxirane

Iron Tricarbonyl Complexes in Oxidation Chemistry: Regio- and Stereoselective Oxyfunctionalization of Trienes by Singlet Oxygen and Dimethyldioxirane

Stoichiometric Applications of Acyclic π-Organoiron Complexes to Organic Synthesis

Highly Stereoselective Total Synthesis of Multiply Protected 3-Amino-3,6-dideoxyaldohexoses (Mycosamine/Mycaminose) by Aldol Condensation Reaction, Mediated by Tin Triflate, of Tricarbonyliron/α-Aminodienone Complexes

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Regio- and Stereocontrolled Synthesis of Terminal 1,3,5-Triene Monoxides via Diene-Iron Tricarbonyl Complexes

Cited by 10 publications

References 0 publications

Iron Tricarbonyl Complexes in Oxidation Chemistry: Regio- and Stereoselective Oxyfunctionalization of Trienes by Singlet Oxygen and Dimethyldioxirane

Iron Tricarbonyl Complexes in Oxidation Chemistry: Regio- and Stereoselective Oxyfunctionalization of Trienes by Singlet Oxygen and Dimethyldioxirane

Stoichiometric Applications of Acyclic &#960;-Organoiron Complexes to Organic Synthesis

Highly Stereoselective Total Synthesis of Multiply Protected 3-Amino-3,6-dideoxyaldohexoses (Mycosamine/Mycaminose) by Aldol Condensation Reaction, Mediated by Tin Triflate, of Tricarbonyliron/α-Aminodienone Complexes

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Stoichiometric Applications of Acyclic π-Organoiron Complexes to Organic Synthesis