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Relay Cross Metathesis for the Iterative Construction of Terpenoids and Synthesis of a Diterpene-Benzoate Macrolide of Biogenetic Relevance to the Bromophycolides

DOI: 10.14469/hpc/6103 Metadata

Created: 2019-09-16 13:42

Last modified: 2020-03-31 16:56

Author: Karim Bahou

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)

Co-author: D. Christopher Braddock

Description

We report a relay cross metathesis (ReXM) reaction for the ascent of the terpenoids in an iterative protocol. The protocol features the cross metathesis of a relay-actuated Δ6,7-functionalized C10-monoterpenoid alcohol with C10-monoterpenoid citral to form a C15-sesquiterpene. Subsequent functional group manipulation allows for the method to be repeated in an iterative fashion. The method is used for the synthesis of a diterpene-benzoate macrolide of biogenetic relevance to the bromophycolide family of natural products.

Members

DOIDescription
10.14469/hpc/5771 (S,E)-3-(5-(Allyloxy)-3-methylpent-3-en-1-yl)-2,2-dimethyloxirane (2)
10.14469/hpc/5772 (S)-9-(3,3-Dimethyloxiran-2-yl)-3,7-dimethylnona-2,6-dienal (4)
10.14469/hpc/5774 (S)-9-(3,3-Dimethyloxiran-2-yl)-3,7-dimethylnona-2,6-dien-1-ol (7)
10.14469/hpc/5779 (S)-3-(9-(Allyloxy)-3,7-dimethylnona-3,7-dien-1-yl)-2,2-dimethyloxirane (8)
10.14469/hpc/5780 (S)-13-(3,3-Dimethyloxiran-2-yl)-3,7,11-trimethyltrideca-2,6,10-trienal (9)
10.14469/hpc/5781 (S)-13-(3,3-Dimethyloxiran-2-yl)-3,7,11-trimethyltrideca-2,6,10-trien-1-ol (10)
10.14469/hpc/5784 Ethyl 4-hydroxy-3-iodobenzoate (12)
10.14469/hpc/5785 Ethyl 4-ethoxy-3-iodobenzoate (13)
10.14469/hpc/5786 Ethyl (E)-3-(3,7-dimethylocta-2,6-dien-1-yl)-4-ethoxybenzoate (14)
10.14469/hpc/5783 (S)-3-(13-Bromo-3,7,11-trimethyltrideca-3,7,11-trien-1-yl)-2,2-dimethyloxirane (15)
10.14469/hpc/5792 Ethyl (S)-3-(13-(3,3-dimethyloxiran-2-yl)-3,7,11-trimethyltrideca-2,6,10-trien-1-yl)-4-ethoxybenzoate (16)
10.14469/hpc/5788 (S)-3-(13-(3,3-Dimethyloxiran-2-yl)-3,7,11-trimethyltrideca-2,6,10-trien-1-yl)-4-ethoxybenzoic acid (17)
10.14469/hpc/5789 (S)-3-(15-Bromo-14-hydroxy-3,7,11,15-tetramethylhexadeca-2,6,10-trien-1-yl)-4-ethoxybenzoic acid (18)
10.14469/hpc/5790 (R)-3-(14-Bromo-15-hydroxy-3,7,11,15-tetramethylhexadeca-2,6,10-trien-1-yl)-4-ethoxybenzoic acid (18a)
10.14469/hpc/5791 (S,7E,11E,15E)-4-(2-Bromopropan-2-yl)-1^4-ethoxy-7,11,15-trimethyl-3-oxa-1(1,3)-benzenacycloheptadecaphane-7,11,15-trien-2-one (19)

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