A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross Metathesis with Trisubstituted Alkenes
DOI: 10.14469/hpc/5737 Metadata
Created: 2019-06-05 10:03
Last modified: 2020-03-30 14:06
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Co-author: D. Christopher Braddock Co-author: Tianyou He Co-author: Zhensheng Shi
Description
Abstract: A retrosynthetic disconnection-reconnection analysis of epoxypolyenes – substrates that can undergo cyclization to podocarpane-type tricycles – reveals relay-actuated Δ6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (E:Z, ca. 2-3:1). The method is further generalized for the cross metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ6,7-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the E-geometrical isomer).
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/5738 | (E)-1-(Allyloxy)-3,7-dimethylocta-2,6-diene ((E)-4) |
| 10.14469/hpc/5820 | (E)-3-(5-(Allyloxy)-3-methylpent-3-en-1-yl)-2,2-dimethyloxirane ((E)-5a) |
| 10.14469/hpc/5741 | (Z)-1-(Allyloxy)-3,7-dimethylocta-2,6-diene ((Z)-4) |
| 10.14469/hpc/5742 | (Z)-3-(5-(Allyloxy)-3-methylpent-3-en-1-yl)-2,2-dimethyloxirane ((Z)-5a) |
| 10.14469/hpc/5743 | (S,E)-8-(Allyloxy)-2,6-dimethyloct-6-ene-2,3-diol ((S)-5b) |
| 10.14469/hpc/5744 | (S,E)-8-(Allyloxy)-2-hydroxy-2,6-dimethyloct-6-en-3-yl benzoate ((S)-5c) |
| 10.14469/hpc/5745 | (S,E)-5-(5-(Allyloxy)-3-methylpent-3-en-1-yl)-2,2,4,4-tetramethyl-1,3-dioxolane ((S)-5d) |
| 10.14469/hpc/5755 | (S)-2,2,4,4-Tetramethyl-5-(3-methylbut-3-en-1-yl)-1,3-dioxolane ((S)-5f) |
| 10.14469/hpc/6317 | (S,E)-5-(5-(Allyloxy)-3-methylpent-3-en-1-yl)-4,4-dimethyl-2-phenyl-1,3,2-dioxaborolane ((S)-5g) |
| 10.14469/hpc/5759 | (4-Methylpent-3-en-1-yl)benzene (7a) |
| 10.14469/hpc/5761 | 1-Methoxy-4-(4-methylpent-3-en-1-yl)benzene (7c) |
| 10.14469/hpc/6318 | 1-Methoxy-3-(4-methylpent-3-en-1-yl)benzene (7d) |
| 10.14469/hpc/6319 | 1-Methoxy-2-(4-methylpent-3-en-1-yl)benzene (7e) |
| 10.14469/hpc/6320 | 1-Methyl-4-(4-methylpent-3-en-1-yl)benzene (7f) |
| 10.14469/hpc/6321 | 1-Chloro-4-(4-methylpent-3-en-1-yl)benzene (7g) |
| 10.14469/hpc/5756 | 2-Methylnon-2-ene (7h) |
| 10.14469/hpc/5760 | 4-Ethyl-2-methyloct-2-ene (7i) |
| 10.14469/hpc/5757 | (2-Methylprop-1-en-1-yl)benzene (7j) |
| 10.14469/hpc/5758 | (3-Methylbut-2-en-1-yl)benzene (7k) |
| 10.14469/hpc/5763 | 2,2-Dimethyl-3-(3-methyl-6-phenylhex-3-en-1-yl)oxirane (8a) |
| 10.14469/hpc/6326 | (S)-2,2,4,4-Tetramethyl-5-(3-methyl-6-phenylhex-3-en-1-yl)-1,3-dioxolane ((S)-8b) |
| 10.14469/hpc/5817 | 3-(6-(4-Methoxyphenyl)-3-methylhex-3-en-1-yl)-2,2-dimethyloxirane (8c) |
| 10.14469/hpc/6322 | 3-(6-(3-Methoxyphenyl)-3-methylhex-3-en-1-yl)-2,2-dimethyloxirane (8d) |
| 10.14469/hpc/6323 | 3-(6-(2-Methoxyphenyl)-3-methylhex-3-en-1-yl)-2,2-dimethyloxirane (8e) |
| 10.14469/hpc/6414 | 2,2-Dimethyl-3-(3-methyl-6-(p-tolyl)hex-3-en-1-yl)oxirane (8f) |
| 10.14469/hpc/6325 | 3-(6-(4-Chlorophenyl)-3-methylhex-3-en-1-yl)-2,2-dimethyloxirane (8g) |
| 10.14469/hpc/5762 | 2,2-Dimethyl-3-(3-methyldec-3-en-1-yl)oxirane (8h) |
| 10.14469/hpc/5764 | 8-(3,3-Dimethyloxiran-2-yl)-6-methyloct-5-en-2-one (8i) |
| 10.14469/hpc/6328 | (S)-4,4-Dimethyl-5-(3-methyl-6-phenylhex-3-en-1-yl)-2-phenyl-1,3,2-dioxaborolane ((S)-8j) |
| 10.14469/hpc/5767 | (S)-6-Methyl-8-(2,2,5,5-tetramethyl-1,3-dioxolan-4-yl)oct-5-en-2-one ((S)-8k) |
| 10.14469/hpc/6329 | (S)-8-(5,5-dimethyl-2-phenyl-1,3,2-dioxaborolan-4-yl)-6-methyloct-5-en-2-one ((S)-8l) |
| 10.14469/hpc/6466 | 2,2-Dimethyl-3-((E)-3-methyl-5-(((E)-5-phenylpent-2-en-1-yl)oxy)pent-3-en-1-yl)oxirane (9a) |
| 10.14469/hpc/6469 | 2,2-Dimethyl-3-((3E)-3-methyl-5-(prop-1-en-1-yloxy)pent-3-en-1-yl)oxirane (10a) |
| 10.14469/hpc/5765 | (S)-2,6-Dimethylhept-6-ene-2,3-diol (5i) and (S,6E)-2,6-Dimethyl-8-(prop-1-en-1-yloxy)oct-6-ene-2,3-diol (10b) |
| 10.14469/hpc/6333 | (2R,4aR,10aS)-6-Methoxy-1,1,4a-trimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthren-2-ol (11) |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.26434/chemrxiv.8267837.v1 | ChemRxiv preprint v1 |
| References | 10.26434/chemrxiv.8267837.v2 | ChemRxiv preprint v2 |
| References | 10.26434/chemrxiv.8267837.v3 | ChemRxiv preprint v3 |