108393-28-8Relevant articles and documents
A cross metathesis approach to the synthesis of the C11-C23 fragment of (-)-16-normethyldictyostatin
Sai Baba,Das, Parthasarathi,Mukkanti,Iqbal, Javed
, p. 7927 - 7930 (2007/10/03)
The synthesis of the C11-C23 fragment 2 of (-)-16-normethyldictyostatin has been achieved by cross metathesis between two olefinic fragments 4 and 5 followed by a reduction of the double bond at C16-C17. Both the olefinic fragments are easily synthesized
Stereocontrol in organic synthesis using silicon-containing compounds. Studies directed towards the synthesis of ebelactone A
Archibald, Sarah C.,Barden, David J.,Bazin, Jerome F.Y.,Fleming, Ian,Foster, Colin F.,Mandal, Ajay K.,Mandal, Amit K.,Parker, David,Takaki, Ken,Ware, Anne C.,Williams, Anne R.B.,Zwicky, Anna B.
, p. 1051 - 1064 (2007/10/03)
Several approaches to the synthesis of ebelactone A 2 are described, culminating in the synthesis of the benzenesulfonate of 2-epi-ebelactone A 161. All the approaches were based on three fragments A, B and C, originally defined in general terms in Scheme 1, but eventually used as the aldehyde 72, the allenylsilane 3 and the aldehyde 139, respectively. They were joined, first B with C, and then B+C with A. In the main routes to fragments A and C, the relative stereochemistry was controlled by highly stereoselective enolate methylations 66 → 67, 68 → 69, and 135 → 136, in each case anti to an adjacent silyl group, and by a highly stereoselective hydroboration of an allylsilane 137 → 138, also anti to the silyl group. The hydroxyl groups destined to be on C-3 and C-11 were unmasked by silyl-to-hydroxy conversions 69 → 70 and 138 → 139 with retention of configuration. The stereochemistry created in the coupling of fragment B to C was controlled by the stereospecifically anti SE2′ reaction between the enantiomerically enriched allenylsilane 3 and the aldehyde 139. The double bond geometry was controlled by syn stereospecific silylcupration 148 → 151, and preserved by iododesilylation 151 → 152 of the vinylsilane with retention of configuration, and Nozaki-Hiyama-Kishi coupling with the aldehyde 72 gave the whole carbon skeleton 153 of ebelactone A with the correct relative configuration, all of which had been controlled by organosilicon chemistry. In the steps to remove the superfluous allylic hydroxyl, an intermediate allyllithium species 156 abstracted the proton on C-2, and its reprotonation inverted the configuration at that atom. Other routes to the fragments A and C were also explored, both successful and unsuccessful, both silicon-based and conventional, and a number of unexpected side reactions were investigated.
Synthesis of stereotriads by oxymercuration of substituted cyclopropylcarbinols.
Cossy,Blanchard,Meyer
, p. 2567 - 2569 (2007/10/03)
[structure: see text] Cyclopropylcarbinol derivatives bearing an adjacent methyl-substituted stereocenter and a remote beta-hydroxy group protected as a pivalate underwent anchimerically assisted regio- and diastereoselective oxymercurations, affording af
