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

Author: Karim Bahou

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

DOIDescription
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 ...DOIDescription
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

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