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Keywords:

  • biosynthetic pathways;
  • computational chemistry;
  • natural products;
  • structure elucidation;
  • total synthesis

Abstract

The first enantioselective synthesis of cytotoxic natural products rigidiusculamides A (ent-21) and B (8) has been achieved by two synthetic routes. The first one is convergent based on the common intermediate 11, obtained through a high yielding SmI2-mediated Reformatsky-type reaction. A highly diastereoselective one-pot Dess–Martin periodinane-mediated bis-oxidation allowed the direct conversion of the diastereomeric mixture of 11 into rigidiusculamide B (8). Isolation of minor diastereomer 21, in combination with computational work, allowed us to suggest the structure of the natural rigidiusculamide A to be 21, as synthesized by the second route. Four diastereomers (7, 7, 22a, and 22b) and an enantiomer (21) of rigidiusculamide A (21) have been synthesized. On the basis of literature precedents and computational work, a biosynthetic pathway for rigidiusculamides A and B was proposed to account for the opposite configuration at C-5 of those two congeners.

Featured Compounds

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  1. 1 - 49
Compound 21
Molecular Weight:251.2784
Molecular Formula:C13H17NO4
InChIKey:BRDPUVOBQMISIO-DMDPSCGWSA-N
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Compound 8
Molecular Weight:249.2625
Molecular Formula:C13H15NO4
InChIKey:LSHJERGXDDEZAD-GWCFXTLKSA-N
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Compound 11
Molecular Weight:325.4015
Molecular Formula:C20H23NO3
InChIKey:UVNVIJZKOGKSLJ-WHDUELSGSA-N
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Compound 7
Molecular Weight:251.2784
Molecular Formula:C13H17NO4
InChIKey:BRDPUVOBQMISIO-GVXVVHGQSA-N
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Compound 22a
Molecular Weight:251.2784
Molecular Formula:C13H17NO4
InChIKey:BRDPUVOBQMISIO-WZRBSPASSA-N
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Compound 22b
Molecular Weight:251.2784
Molecular Formula:C13H17NO4
InChIKey:BRDPUVOBQMISIO-NTZNESFSSA-N
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Compound ent-21
Molecular Weight:251.2784
Molecular Formula:C13H17NO4
InChIKey:BRDPUVOBQMISIO-MDZLAQPJSA-N
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Compound 1
Molecular Weight:297.3484
Molecular Formula:C18H19NO3
InChIKey:WGYGSZOQGYRGIP-NCOADZHNSA-N
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Compound 2
Molecular Weight:376.425
Molecular Formula:C15H24N2O7S
InChIKey:DAQAKHDKYAWHCG-NSUSRNALSA-N
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Compound 3
Molecular Weight:213.2304
Molecular Formula:C10H15NO4
InChIKey:FWPWHHUJACGNMZ-NBBQQVJHSA-N
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Compound 4
Molecular Weight:313.777
Molecular Formula:C15H20ClNO4
InChIKey:NGWSFRIPKNWYAO-SHTIJGAHSA-N
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Compound 5
Molecular Weight:476.05
Molecular Formula:C15H21Cl6NO3
InChIKey:SZYKZXUJGUQVIX-QAEOJHPCSA-N
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Compound 6
Molecular Weight:191.2264
Molecular Formula:C11H13NO2
InChIKey:AFEUCARVKFDANA-UWVGGRQHSA-N
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Compound ent-7
Molecular Weight:251.2784
Molecular Formula:C13H17NO4
InChIKey:BRDPUVOBQMISIO-NQBHXWOUSA-N
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Compound 9
Molecular Weight:333.3789
Molecular Formula:C18H23NO5
InChIKey:FSANWLZUMUEFDI-PKZGSEHASA-N
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Compound 10
Molecular Weight:335.3948
Molecular Formula:C18H25NO5
InChIKey:YSTJGABLVSIEEQ-UJILACHPSA-N
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Compound 12
Molecular Weight:471.5858
Molecular Formula:C27H37NO6
InChIKey:RZLBURMQWWOSET-JWLIYLPMSA-N
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Compound 14
Molecular Weight:181.028
Molecular Formula:C5H9BrO2
InChIKey:ARFLASKVLJTEJD-UHFFFAOYSA-N
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Compound 11a
Molecular Weight:325.4015
Molecular Formula:C20H23NO3
InChIKey:UVNVIJZKOGKSLJ-CCKFTAQKSA-N
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Compound 11b
Molecular Weight:325.4015
Molecular Formula:C20H23NO3
InChIKey:UVNVIJZKOGKSLJ-ZOCIIQOWSA-N
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Compound 11c
Molecular Weight:325.4015
Molecular Formula:C20H23NO3
InChIKey:UVNVIJZKOGKSLJ-MDASCCDHSA-N
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Compound 11d
Molecular Weight:325.4015
Molecular Formula:C20H23NO3
InChIKey:UVNVIJZKOGKSLJ-JVPBZIDWSA-N
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Compound 16
Molecular Weight:339.385
Molecular Formula:C20H21NO4
InChIKey:XQNGEZXOIIYFAZ-PXNSSMCTSA-N
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Compound 17
Molecular Weight:403.492
Molecular Formula:C21H25NO5S
InChIKey:KVIVFGXLJFKZFA-YHDJDMAPSA-N
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Compound 18
Molecular Weight:307.3862
Molecular Formula:C20H21NO2
InChIKey:ZJYUOEMDGWOONU-GOSISDBHSA-N
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Compound 19
Molecular Weight:341.4009
Molecular Formula:C20H23NO4
InChIKey:KHRQHMPANSANMJ-BJLQDIEVSA-N
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Compound 20
Molecular Weight:341.4009
Molecular Formula:C20H23NO4
InChIKey:KHRQHMPANSANMJ-NLWGTHIKSA-N
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Compound R-13
Molecular Weight:369.4541
Molecular Formula:C22H27NO4
InChIKey:MUMWMSQTUJMYBC-LJQANCHMSA-N
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Compound 23a
Molecular Weight:453.5705
Molecular Formula:C27H35NO5
InChIKey:DWZXHMQNEOZVAZ-JVIWHDFBSA-N
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Compound 23b
Molecular Weight:453.5705
Molecular Formula:C27H35NO5
InChIKey:DWZXHMQNEOZVAZ-IWXARTOSSA-N
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Compound 24a
Molecular Weight:487.5852
Molecular Formula:C27H37NO7
InChIKey:SRBPQZIMNOAUCB-NOTUOJBMSA-N
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Compound 24b
Molecular Weight:487.5852
Molecular Formula:C27H37NO7
InChIKey:SRBPQZIMNOAUCB-KHVXQDHOSA-N
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Compound 25a
Molecular Weight:341.4009
Molecular Formula:C20H23NO4
InChIKey:KHRQHMPANSANMJ-GGPKGHCWSA-N
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Compound 25b
Molecular Weight:341.4009
Molecular Formula:C20H23NO4
InChIKey:KHRQHMPANSANMJ-WSTZPKSXSA-N
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Compound 24c
Molecular Weight:487.5852
Molecular Formula:C27H37NO7
InChIKey:SRBPQZIMNOAUCB-AZSVPQILSA-N
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Compound 24d
Molecular Weight:487.5852
Molecular Formula:C27H37NO7
InChIKey:SRBPQZIMNOAUCB-KHVXQDHOSA-N
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Compound 27a
Molecular Weight:425.4743
Molecular Formula:C24H27NO6
InChIKey:XPHNQTNMLYXWCX-CQOQZXRMSA-N
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Compound 27b
Molecular Weight:425.4743
Molecular Formula:C24H27NO6
InChIKey:XPHNQTNMLYXWCX-GPXNEJASSA-N
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Compound 26a
Molecular Weight:341.4009
Molecular Formula:C20H23NO4
InChIKey:KHRQHMPANSANMJ-QWFCFKBJSA-N
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Compound 26b
Molecular Weight:341.4009
Molecular Formula:C20H23NO4
InChIKey:KHRQHMPANSANMJ-HBFSDRIKSA-N
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Compound 30
Molecular Weight:173.2096
Molecular Formula:C8H15NO3
InChIKey:FXUAIOOAOAVCGD-WCTZXXKLSA-N
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Compound 28
Molecular Weight:157.2102
Molecular Formula:C8H15NO2
InChIKey:SQECYPINZNWUTE-RNJXMRFFSA-N
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Compound 29
Molecular Weight:156.2254
Molecular Formula:C8H16N2O
InChIKey:FUEOWQNIWDQPQO-FXQIFTODSA-N
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Compound 31
Molecular Weight:286.583
Molecular Formula:C10H14Cl3NO2
InChIKey:FGAIQUBOQVNVPA-UHFFFAOYSA-N
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Compound 32
Molecular Weight:349.4644
Molecular Formula:C20H31NO4
InChIKey:QHXAUDQIMHYILR-LPQFERQCSA-N
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Compound A
Molecular Weight:233.2631
Molecular Formula:C13H15NO3
InChIKey:ONSPRDXXARMPJH-LYNSQETBSA-N
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Compound B
Molecular Weight:249.2625
Molecular Formula:C13H15NO4
InChIKey:LSHJERGXDDEZAD-MFKMUULPSA-N
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Compound 33
Molecular Weight:265.305
Molecular Formula:C14H19NO4
InChIKey:YKJYKKNCCRKFSL-RDBSUJKOSA-N
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Compound 34
Molecular Weight:317.5087
Molecular Formula:C21H35NO
InChIKey:GBCXKHLKJHRTAB-HKBOAZHASA-N
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  1. 1 - 49