A formal synthesis of (+)-madindoline A was achieved. The Sunazuka's key intermediate (4R,5S)-(–)-3-butyl-4-(tert-butyldimethylsiloxy)-5-methoxycarbonyl-2,5-dimethyl-2-cyclopentenone was synthesized from easily available (2S,3S)-3-acetoxy-2-ethenyl-2-methylcyclopentanone. The starting material was reliably supplied by a chemo-enzymatic procedure in enantiomerically pure form. The synthesis was performed by straightforward transformations involving enone formation and regioselective introduction of the two alkyl side chains.
HayashiM, KimYP, TakamatsuS, EnomotoA, ShinoseM, TakahashiY, TanakaH, KomiyamaK, ŌmuraS. (1996) Madindoline, a novel inhibitor of IL-6 activity from Streptomyces sp. K93-0711. I. Taxonomy, fermentation, isolation and biological activities. Journal of Antibiotics, 49, 1091–1095.
2.
ZhangXG, BatailleR, JourdanM, SaelandS, BanchereauJ, MannoniP, KleinB., (1990) Granulocyte-macrophage colony-stimulating factor synergizes with interleukin-6 in supporting the proliferation of human myeloma cells. Blood, 76, 2599–2605.
SunazukaS, HiroseT, ShirahataT, HarigayaY, HayashiM, KomiyamaK, ŌmuraS. (2000) Total synthesis of (+)-madindoline A and (–)-madindoline B, potent, selective inhibitors of interleukin 6. Determination of the relative and absolute configurations. Journal of the American Chemical Society, 122, 2122–2123;
5.
HiroseT, SunazukaT, ShirahataT, YamamotoD, HarigayaY, KuwajimaI, ŌmuraS. (2002) Short total synthesis of (+)-madindolines A and B. Organic Letters, 4, 501–503;
6.
HiroseT, SunazukaT, YamamotoD, KojimaN., ShirahataT, HarigayaY, KuwajimaI, ŌmuraS. (2005) Determination of the absolute stereochemistry and asymmetric total synthesis of madindolines A and B: a practical improvement to a second-generation approach from the first-generationTetrahedron, 61, 6015–6039.
7.
HosokawaS, SekiguchiK, EnomotoM, KobayashiS., (2000) Novel stereoselective construction of a quaternary carbon: application to synthesis of the cyclopentenedione moiety of madindolines. Tetrahedron Letters, 41, 6429–6433;
8.
HosokawaS, SekiguchiK, HayaseK, HirukawaY, KobayashiS., (2000) Total synthesis of madindoline A. Tetrahedron Letters, 41, 6435–6439.
9.
McComasCC, PeralesJB, Van VrankenDL. (2002) Synthesis of (±)-madindolines and chemical models. Studies of chemical reactivity. Organic Letters, 4, 2337–2340.
10.
WanL, TiusMA. (2007) Synthesis of (+)-madindoline A and (+)-madindoline B. Organic Letters, 9, 647–650.
11.
FuhshukuK, FunaN, AkeboshiT, OhtaH, HosomiH, OhbaS, SugaiT., (2000) Access to Wieland-Miescher ketone in an enantiomerically pure form by a kinetic resolution with yeast-mediated reduction. The Journal of Organic Chemistry, 65, 129–135;
12.
FuhshukuK, TomitaM, SugaiT., (2004) Unprecedented chemo-enzymatic synthesis of stereochemically pure 3-acetoxy-2-methyl-2-vinylcycloalkanones. Tetrahedron Letters, 45, 1763–1767.
13.
MitsunobuO, YamadaM., (1967) Preparation of esters of carboxylic and phosphoric acid via quaternary phosphonium salts. Bulletin of the Chemical Society of Japan, 40, 2380–2382;
14.
SwamyKCK, KumarNNB, BalaramanE, KumarKVPP. (2009) Mitsunobu and related reactions: Advances and applications. Chemical Reviews, 109, 2551–2651, and references cited therein.
15.
ItoY, HiraoT, SaegusaT., (1978) Synthesis of α, β-unsaturated carbonyl compounds by palladium(I1)-catalyzed dehydrosilylation of silyl enol ethers. The Journal of Organic Chemistry, 43, 1011–1013;
16.
LarockRC, HightowerT, KrausGA, HahnP, ZhengD., (1995) A simple, effective, new, palladium-catalyzed conversion of enol silanes to enones and enals. Tetrahedron Letters, 36, 2423–2426.
17.
HartungR, PaquetteLA. (2005) Practical synthesis of enantiopure spiro[4.4]nonane C-(2‘-deoxy)ribonucleosides. The Journal of Organic Chemistry, 70, 1597–1604.
18.
ChavanSP, ZubaidhaPK, DhondgeVD. (1993) A short and efficient synthesis of (-) mintlactone and (+) iso-mintlactoneTetrahedron, 49, 6429– 6436.
