Rapid assembly of the bicyclo[5.3.1]undecenone core of penostatin F: a successive Diels-Alder/Claisen reaction strategy with an efficient stereochemical relay.

The first synthesis of the tricyclic core of Penostatin F (1) using a stereocontrolled Diels-Alder reaction and a Claisen rearrangement in succession has been achieved in nine steps from commercially available methyl acetoacetate and (E)-2-decenal. Penostatin F is a metabolite isolated from a fungal strain of Penicillium sp., OUPS-79, separated from the marine alga Enteromorphia intestinalis and exhibits significant cytotoxicity against cultured P388 Leukemia cells (ED(50) = 1.4 micromol/mL). [reaction: see text]

[1]  I. Mcdonald,et al.  The art of innovation in organic chemistry: synthetic efforts toward the phomoidrides. , 2003, Chemical reviews.

[2]  Roxanne Clément,et al.  Highly stereoselective hydroxy-directed Diels-Alder reaction. , 2003, The Journal of organic chemistry.

[3]  Ward,et al.  Intramolecular diels-alder reaction by self-assembly of the components on a lewis acid template , 2000, Organic letters.

[4]  M. Shair,et al.  A Highly Efficient and Convergent Reaction for the Synthesis of Bridgehead Enone‐Containing Polycyclic Ring Systems , 2000 .

[5]  Bertozzi,et al.  Temporary in situ aluminum and zinc tethering in Diels-Alder reactions , 2000, Organic letters.

[6]  R. Batey,et al.  Alkenylboronate Tethered Intramolecular Diels−Alder Reactions , 1999 .

[7]  K. Shea,et al.  Disposable tethers in synthetic organic chemistry , 1998 .

[8]  O. Daugulis,et al.  Dual Activation in the Esterification of Hindered Alcohols with Anhydrides Using MgBr2 and a Tertiary Amine , 1996 .

[9]  G. Stork,et al.  Temporary Magnesium and Aluminum Connections in [4 + 2] Cycloadditions , 1995 .

[10]  K. Nicolaou,et al.  Total Synthesis of Taxol. 4. The Final Stages and Completion of the Synthesis , 1995 .

[11]  K. Narasaka,et al.  Boron Compound as a Trapping Reagent of α-Hydroxy o-Quinodimethanes in the Diels–Alder Reaction , 1993 .

[12]  S. Sieburth,et al.  An intramolecular Diels-Alder reaction of vinylsilanes , 1992 .

[13]  G. Breault,et al.  The temporary silicon connection in the control of the regiochemistry of 4 + 2 cycloadditions , 1992 .

[14]  N. Iwasawa,et al.  Phenylboronic Acid as a Template in the Diels-Alder Reaction , 1991 .

[15]  K. Tamao,et al.  Nickel(0)-catalyzed cyclization of 1,7-diynes via hydrosilation: one-step synthesis of 1,2-dialkylidenecyclohexanes with a (Z)-vinylsilane moiety , 1989 .

[16]  A. Numata,et al.  Cytotoxic triterpenes from a Chinese medicine, Goreishi. , 1989, Chemical & pharmaceutical bulletin.

[17]  E. Carreira,et al.  Directed reduction of .beta.-hydroxy ketones employing tetramethylammonium triacetoxyborohydride , 1988 .

[18]  L. Weiler,et al.  Alkylation of dianions of .beta.-keto esters , 1974 .