α‐Oxygenated Crotyltitanium and Dyotropic Rearrangement in the Total Synthesis of Discodermolide

Lemos, Elsa De; Porée, François‐Hugues; Commerçon, Alain; Betzer, Jean‐François; Pancrazi, Ange; Ardisson, Janick

doi:10.1002/ange.200604629

Cited by 13 publications

(1 citation statement)

References 83 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this full account, we report synthetic details of our total synthesis of DDM ( 1 ), including related alternative synthetic approaches that enabled us to develop the final effective synthetic route 7. The modulable character of this approach might allow structural modifications of DDM and, therefore, the elaboration and investigation of novel discodermolide structural analogues.…”

Section: Introductionmentioning

confidence: 99%

Total Synthesis of Discodermolide: Optimization of the Effective Synthetic Route

Lemos

Porée

Bourin

et al. 2008

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

An efficient and modulable total synthesis of discodermolide (DDM), a unique marine anticancer polyketide is described including related alternative synthetic approaches. Particularly notable is the repeated application of a crotyltitanation reaction to yield homoallylic (Z)-O-ene-carbamate alcohols with excellent selectivity. Advantage was taken of this reaction not only for the stereocontrolled building of the syn-anti methyl-hydroxy-methyl triads of DDM, but also for the direct construction of the terminal (Z)-diene. Of particular interest is also the installation of the C13=C14 (Z)-double bond through a highly selective dyotropic rearrangement. The preparation of the middle C8-C14 fragment in two sequential stages and its coupling to the C1-C7 moiety was a real challenge and required careful optimization. Several synthetic routes were explored to allow high and reliable yields. Due to the flexibility and robust character of this approach, it might enable a systematic structural variation of DDM and, therefore, the elaboration and exploration of novel discodermolide structural analogues.

show abstract

Section: Introductionmentioning

confidence: 99%

Total Synthesis of Discodermolide: Optimization of the Effective Synthetic Route

Lemos

Porée

Bourin

et al. 2008

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

Palladium‐Catalyzed Three‐Component Reaction of 3‐(Tri‐n‐ butylstannyl)allyl Acetates, Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ‐Substituted Allylic Tin Reagents

2016

View full text Add to dashboard Cite

show abstract

Synthesis of C9‐C13 and C15‐C21 Subunits of Discodermolide

Kaliappan

2020

Asian J Org Chem

View full text Add to dashboard Cite

A new synthetic strategy for the construction of two polypropionate subunits of discodermolide, a highly potent anticancer natural product, is reported. The strategy relies on two key reactions: a Shimizu non‐aldol reaction, a stereoselective hydrogenolysis of alkenyl epoxides, to generate the syn hydroxy‐methyl moiety and a NaBH4‐BF3.OEt2 mediated hydride addition reaction. By utilizing this strategy, two different fragments of discodermolide, C9‐C13 subunit and C15‐C21 subunit have been successfully synthesized.

show abstract

α‐Oxygenated Crotyltitanium and Dyotropic Rearrangement in the Total Synthesis of Discodermolide

Cited by 13 publications

References 83 publications

Total Synthesis of Discodermolide: Optimization of the Effective Synthetic Route

Total Synthesis of Discodermolide: Optimization of the Effective Synthetic Route

Palladium‐Catalyzed Three‐Component Reaction of 3‐(Tri‐n‐ butylstannyl)allyl Acetates, Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ‐Substituted Allylic Tin Reagents

Synthesis of C9‐C13 and C15‐C21 Subunits of Discodermolide

Contact Info

Product

Resources

About