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-1991-20719

Cited by 14 publications

(1 citation statement)

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“…[9] However, the electrophilic amination of the lithium enolate or silyl enol ethers of this ketone, using lithium tertbutyl-N-tosyloxycarbamate (LiBTOC), according to Genet's procedure, [10,11] was unsuccessful. [12] The synthesis of an N-BOC-protected α-aminodienone by direct substitution of the bromine atom of the known bromodienone complex 2 by a tert-butylcarbamate group also failed.…”

Section: Resultsmentioning

confidence: 99%

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

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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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Section: Resultsmentioning

confidence: 99%