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. 2009;48(34):6293-5.
doi: 10.1002/anie.200901992.

Rhodium-catalyzed asymmetric enyne cycloisomerization of terminal alkynes and formal total synthesis of (-)-platensimycin

K C Nicolaou  1 , Ang Li, Shelby P Ellery, David J Edmonds
Affiliations

Rhodium-catalyzed asymmetric enyne cycloisomerization of terminal alkynes and formal total synthesis of (-)-platensimycin

K C Nicolaou et al. Angew Chem Int Ed Engl. 2009.
No abstract available

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Figures

Scheme 1
Scheme 1
Proposed mechanism of Rh-catalyzed asymmetric cycloisomerization of terminal enynes.
Scheme 2
Scheme 2
Preparation and X-ray crystallographic analysis of p-bromophenyl carbamate 1b. Reagents and conditions: a) NaBH4 (1.5 equiv), EtOH, 0 °C, 15 min; b) p-bromophenyl isocyanate (1.05 equiv), Et3N (1.05 equiv), 0 °C, 1 h, 72 % over two steps. Non-hydrogen atoms are shown as 30 % ellipsoids.
Scheme 3
Scheme 3
Formal total synthesis of (−)-platensimycin. Reagents and conditions: a) DIBAL-H (1.0 M in hexanes, 1.2 equiv), THF, −78 → −20 °C, 1 h; then 2 N aq. HCl, 0 °C, 30 min, 88 %; b) TMSOTf (1.2 equiv), Et3N (1.5 equiv), CH2Cl2, 0 °C, 30 min; c) IBX (1.2 equiv), MPO (1.2 equiv), DMSO, 23 °C, 3 h; d) 1 N aq. HCl, THF, 0 °C, 1 h, 68 % over three steps; e) [Rh((S)-BINAP)]SbF6 (0.05 equiv), DCE, 23 °C, 12 h, 86 %, > 99 % ee. DIBAL-H = diisobutylaluminum hydride, DMSO = dimethyl sulfoxide, IBX = o-iodoxybenzoic acid, MPO = 4-methoxypyridine-N-oxide.
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