A short synthesis of (-)-dendrobine. Some observations on the nickel mediated radical cyclisation and on the Pauson-Khand reaction

Abstract : The total synthesis of (-)-dendrobine was accomplished in 13 steps starting from (+)-verbenol. The key step is a radical cascade starting with a carbamyl radical generated by reaction of the N-benzoyloxy-carbamyl derivative of trans-verbenol with tributylstannane. This allows the one step establishment of three contiguous stereogenic centres, including the difficult cis-vicinal amino alcohol motif, and ultimately the control of the configuration of the remaining four asymmetric carbons. The synthesis also features the use of the Pauson-Khand reaction where an interesting solvent effect was observed. Thus, the use of a coordinating solvent such as acetonitrile was found necessary to suppress the formation of a ring-opened by-product resulting from scission of a C-N bond. In an ancillary model study, we observed an unusual but interesting 1,4-hydrogen atom abstraction which, however, thwarted our initial synthetic plan. © 2001 Published by Elsevier Science B.V.
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Journal of Organometallic Chemistry, Elsevier, 2001, 624 (40940), pp.316-326. 〈10.1016/s0022-328x(01)00662-3〉
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Soumis le : jeudi 13 mars 2014 - 21:20:54
Dernière modification le : jeudi 10 mai 2018 - 02:07:29

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J. Cassayre, Samir Zard. A short synthesis of (-)-dendrobine. Some observations on the nickel mediated radical cyclisation and on the Pauson-Khand reaction. Journal of Organometallic Chemistry, Elsevier, 2001, 624 (40940), pp.316-326. 〈10.1016/s0022-328x(01)00662-3〉. 〈hal-00954871〉

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