Lyngbouilloside and the related macrolides lyngbyaloside lyngbyaloside B and lyngbyaloside C have attracted a lot of attention over the past decade due to their intriguing architecture their natural scarcity and their potential biological activities. This review aims to showcase the various strategies that have been used to access these natural products.
TanLT. (2007) Bioactive natural products from marine cyanobacteria for drug discovery. Phytochemistry, 68, 954–979;
2.
BurjaAM, BanaigsB, Abou-MansourE, BurgessJG, WrightPC. (2001) Marine cyanobacteria - A prolific source of natural products. Tetrahedron, 57, 9347–9377;
3.
GademannK, PortmannC., (2008) Secondary metabolites from cyanobacteria: complex structures and powerful bioactivities. Current Organic Chemistry, 12, 326–341;
4.
WilliamsPG. (2009) Panning for chemical gold: marine bacteria as a source of new therapeutics. Trends in Biotechnology, 27, 45–52;
5.
NunneryJK, MeversE, GerwickWH. (2010) Biologically active secondary metabolites from marine cyanobacteria. Current Opinion in Biotechnology, 21, 787–793;
6.
GerwickWH, MooreBS. (2012) Lessons from the past and charting the future of marine natural products drug discovery and chemical biology. Chemistry & Biology, 19, 85–98.
7.
KleinD, BraekmanJC, DalozeD, HoffmannL, CastilloG, DemoulinV. (1999) Lyngbyapeptin A, a modified tetrapeptide from Lyngbya bouillonii (Cyanophyceae). Tetrahedron Letters, 40, 695–696.
8.
KleinD, BraekmanJC, DalozeD, HoffmannL, DemoulinV., (1996) Laingolide, a novel 15-membered macrolide from Lyngbya bouillonii (Cyanophyceae). Tetrahedron Letters, 37, 7519–7520;
9.
KleinD, BraekmanJC, DalozeD, HoffmannL, CastilloG, DemoulinV., (1999) Madangolide and laingolide A, two novel macrolides from Lyngbya bouillonii (Cyanobacteria). Journal of Natural Products, 62, 934–936.
10.
TanLT, MárquezBL, GerwickWH. (2002) Lyngbouilloside, a novel glycosidic macrolide from the marine cyanobacterium Lyngbya bouillonii. Journal of Natural Products, 65, 925–928.
11.
KleinD, BraekmanJC, DalozeD, HoffmannL, DemoulinV., (1997) Lyngbyaloside, a novel 2,3,4-tri-O-methyl-6-deoxy-α-mannopyranoside macrolide from Lyngbya bouillonii (Cyanobacteria). Journal of Natural Products, 60, 1057–1059.
12.
MatthewS, SalvadorL, SchuppPJ, PaulVJ, LueschH. (2010) Cytotoxic halogenated macrolides and modified peptides from the apratoxin-producing marine cyanobacterium Lyngbya bouillonii from Guam. Journal of Natural Products, 73, 1544–1552.
13.
LueschH, YoshidaWY, HarriganGG, DoomJP, MooreRE, PaulVJ. (2002) Lyngbyaloside B, a new glycoside macrolide from a palauan marine cyanobacterium, Lyngbya sp. Journal of Natural Products, 65, 1945–1948.
14.
HoffmannL, DemoulinV., (1991) Marine cyanophyceae of Papua New Guinea. II. Lyngbya bouillonii sp. nov., a remarkable tropical reef-inhabiting blue-green alga. Belgian Journal of Botany, 124, 82–88.
15.
SoneH, KigoshiH, YamadaK., (1996) Aurisides A and B, cytotoxic macrolide glycosides from the Japanese sea hare Dolabella auricularia. The Journal of Organic Chemistry, 61, 8956–8960.
16.
WebbD, Van den HeuvelA, KöglM, LeySV. (2009) Enantioselective synthesis of the lyngbouilloside macrolactone core. Synlett, 2320–2324.
17.
HongSH, SandersDP, LeeCW, GrubbsRH. (2005) Prevention of undesirable isomerization during olefin metathesis. Journal of the American Chemical Society, 127, 17160–17161.
18.
SneddonHF, GauntMJ, LeySV. (2003) Addition of dithiols to bis-ynones: development of a versatile platform for the synthesis of polyketide natural products. Organic Letters, 5, 1147–1150;
19.
GauntMJ, SneddonHF, HewittPR, OrsiniP, HookDF, LeySV. (2003) Development of β-keto 1,3-dithianes as versatile intermediates for organic synthesis. Organic & Biomolecular Chemistry, 1, 15–16;
20.
SneddonHF, Van den HeuvelA, HirschAKH, BoothRA, ShawDM, GauntMJ, LeySV. (2006) Double conjugate addition of dithiols to propargylic carbonyl systems to generate protected 1,3-dicarbonyl compounds. The Journal of Organic Chemistry, 71, 2715–2725.
21.
MaguireRJ, MuntSP, ThomasEJ. (1998) An approach to the C(10)–C(16) fragment of the bryostatins: stereoselective exocyclic double-bond formation by vinyl radical cyclization. Journal of the Chemical Society, Perkin Transactions1, 2853–2864.
22.
AdderleyNJ, BuchananDJ, DixonDJ, LaineDI. (2003) Highly diastereoselective oxy-Michael additions of enantiopure δ-lactol anions to nitroalkenes: asymmetric synthesis of 1,2-amino alcohols. Angewandte Chemie International Edition, 42, 4241–4244.
23.
GebauerJ, ArseniyadisS, CossyJ., (2008) Facile synthesis of the C1-C13 fragment of lyngbouilloside. Synlett, 712–714.
24.
ReberKP, TilleySD, SorensenEJ. (2009) Bond formations by intermolecular and intramolecular trappings of acylketenes and their applications in natural product synthesis. Chemical Society Reveiws, 38, 3022–3034;
25.
GebauerJ, BlechertS., (2006) Synthesis of y,δ-unsaturated-β-keto lactones via sequential cross metathesis-lactonization: A facile entry to macrolide antibiotic (-)-A26771B. The Journal of Organic Chemistry, 71, 2021–2025;
26.
HoyeTR, DanielsonME, MayAE, ZhaoH., (2008) Dual macrolactonization/pyran-hemiketal formation via acylketenes: applications to the synthesis of (-)-callipeltoside A and a lyngbyaloside B model system. Angewandte Chemie International Edition, 47, 9743–9746.
27.
BachT, KirschS., (2001) Synthesis of 6-substituted 4-hydroxy-2-pyrones from aldehydes by addition of an acetoacetate equivalent, Dess–Martin oxidation and subsequent cyclization. Synlett, 1974–1976.
28.
GrunwellJR, KaripidesA, WigalCT, HeinzmanSW, ParlowJ, SursoJA, ClaytonL, FleitzFJ, DaffnerM, StevensJE. (1991) The formal oxidative addition of electron-rich transoid dienes to bromonaphthoquinones. The Journal of Organic Chemistry, 56, 91–95;
29.
SugitaY, SakakiJI, SatoM, KanekoC., (1992) Use of 1,3-dioxin-4-ones and related compounds in synthesis. Part 39. Enantioselective synthesis of 1,3-dioxin-4-ones having 2,3-dihydroxy- or 2,3,4-trihydroxyalkyl groups at the 6-position: versatile building blocks of polyhydroxylated 4-7 carbon backbonesJournal of the Chemical Society, Perkin Transactions1, 2855–2861.
30.
The absolute configuration was secured by hydrogenation of the terminal double bond and comparison of the optical rotation of the product {[α]D20: −21.0 (c 0.1, CHCl3)} with the one reported in the literature {[α]D20: +19.0 (CHCl3)}, see: SatoM, SunamiS, SugitaY, KanekoC., (1995) An efficient asymmetric aldol reaction of 4-trimethylsiloxy-6-methylene-1,3-dioxinones by chiral binaphthol-titanium complex catalysis. Heterocycles, 41, 1435–1444.
31.
DuthalerRO, HafnerA., (1992) Chiral titanium complexes for enantioselective addition of nucleophiles to carbonyl groups. Chemical Reviews, 92, 807–832.
32.
EvansDA, ChapmanKT. (1986) The directed reduction of β-hydroxy ketones employing Me4NHB(OAc)3. Tetrahedron Letters, 27, 5939–5942.
ElMarrouniA, LebeufR, GebauerJ, HerasM, ArseniyadisS, CossyJ., (2012) Total synthesis of nominal lyngbouilloside aglycon. Organic Letters, 14, 314–317.
35.
EvansDA, MurryJA, KozlowskiMC. (1996) C2-Symmetric copper(II) complexes as chiral Lewis acids. Catalytic enantioselective aldol additions of silylketene acetals to (benzyloxy)acetaldehyde. Journal of the American Chemical Society, 118, 5814–5815;
36.
KrügerJ, CarreiraEM. (1998) Apparent catalytic generation of chiral metal enolates: enantioselective dienolate additions to aldehydes mediated by Tol-BINAPCu(II) fluoride complexes. Journal of the American Chemical Society, 120, 837–838;
37.
PagenkopfBL, KrügerJ, StojanovicA, CarreiraEM. (1998) Mechanistic insights into Cu-catalyzed asymmetric aldol reactions: chemical and spectroscopic evidence for a metalloenolate intermediateAngewandte Chemie International Edition, 37, 3124–3126;
38.
EvansDA, KozlowskiMC, MurryJA, BurgeyCS, CamposKR, ConnellBT, StaplesRJ. (1999) C2-Symmetric copper(II) complexes as chiral Lewis acids. Scope and mechanism of catalytic enantioselective aldol additions of enolsilanes to (benzyloxy)acetaldehyde. Journal of the American Chemical Society, 121, 669–685;
BluetG, CampagneJM. (2001) Catalytic asymmetric vinylogous Mukaiyama-aldol (CAVM) reactions: the enolate activation. The Journal of Organic Chemistry, 66, 4293–4298.
41.
De RosaM, AcocellaMR, VillanoR, SorienteA, ScettriA., (2003) A convenient catalytic procedure for the highly enantioselective aldol condensation of O-silyldienolates. Tetrahedron: Asymmetry, 14, 2499–2502.
42.
MitsunobuO, YamadaY., (1967) Preparation of esters of carboxylic and phosphoric acid via quaternary phosphonium salts. Bulletin of the Chemical Society of Japan, 40, 2380–2382.
43.
JacobsenEN, MarkoI, MungallWS, SchroederG, SharplessKB. (1988) Asymmetric dihydroxylation via ligand-accelerated catalysis. Journal of the American Chemical Society, 110, 1968–1970;
44.
KolbHC, Van NieuwenhzeMS, SharplessKB. (1994) Catalytic asymmetric dihydroxylation. Chemical Reviews, 94, 2483–2547.
45.
The selectivity of the Sharpless dihydroxylation was determined by chiral SFC analysis of the corresponding epoxide 46 (CHIRALCEL OD-H, 100 bar, 5 mL.min−1, 5% MeOH). This result was in absolute accordance with the studies performed by Tietze et al. who demonstrated that the nature of the protecting group had a strong influence on the enantioselectivity of the dihydroxylation, see: TietzeLF, GörlitzerJ. (1998) Preparation of chiral building blocks for a highly convergent vitamin E synthesis. Systematic investigations on the enantioselectivity of the Sharpless bishydroxylation. Synthesis, 873–878.
46.
AnikinA, MaslovM, SieleJ, BlaurockS, BaldamusJ, HennigL, FindeisenM, ReinhardtG, OehmeR, WelzelP., (2003) Synthesis of a 1α-amino-1-deoxy analogue of forskolin. Tetrahedron, 59, 5295–5306;
47.
SparksSM, ChenCL, MartinSF. (2007) Tandem intramolecular benzyne–furan cycloadditions. Total synthesis of vineomycinone B2 methyl ester. Tetrahedron, 63, 8619–8635.
48.
Allenylmagnesium bromide was generated in situ from propargyl bromide and metallic magnesium in the presence of a catalytic amount of HgCl2, see: (a) NakayamaY, KumarGB, KobayashiY., (2000) Synthesis of 10,11-dihydroleukotriene B4 metabolites via a nickel-catalyzed coupling reaction of cis-bromides and trans-alkenyl borates. The Journal of Organic Chemistry, 65, 707–715;
49.
DmitrievaLL, NikitinaLP, AlbanovAI, NedolyaNA. (2005) Vinyl ethers containing an epoxy group: XXIII. Reactions of alkynylmagnesium bromides with glycidol ethers: synthesis and thermal transformations of 1-[2-(vinyloxy)ethoxy]- and 1-(allyloxy)-5-hexyn-2-ols, −5-phenyl-4-pentyn-2-ols, and −3-bromo-2-propanols. Russian Journal of Organic Chemistry, 41, 1583–1593.
50.
FuwaH, NotoK, SasakiM., (2010) Stereoselective synthesis of substituted tetrahydropyrans via domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization. Organic Letters, 12, 1636–1639.
51.
LipshutzBH, UngCS, SenguptaS., (1989) 1,4-Reductions of α,β-unsaturated ketones and aldehydes via in situ generated hydridocuprates. Synlett, 64–66.
52.
OikawaY, YoshiokaT, YonemitsuO., (1982) Protection of hydroxy groups by intramolecular oxidative formation of methoxybenzylidene acetals with DDQ. Tetrahedron Letters, 23, 889–892.
53.
For a recent application of the acylketene dual macrolactonization/pyran hemiketal formation reaction, see: (f) TrostBM, GunznerJL. (2001) Total synthesis of deschlorocallipeltoside A. Journal of the American Chemical Society, 123, 9449–9450.
54.
TrostBM, GunznerJLDiratO, RheeYH. (2002) Callipeltoside A: total synthesis, assignment of the absolute and relative configuration, and evaluation of synthetic analogues. Journal of the American Chemical Society, 124, 10396–10415.
55.
KimS, KimB, InJ. (2009) Facile deprotection of bulky (trialkylsilyl)acetylenes with silver fluoride. Synthesis, 12, 1963–1968.
56.
SonogashiraK, TohdaY, HagiharaN., (1975) A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetrahedron Letters, 16, 4467–4470;
57.
ChinchillaR, NájeraC. (2007) The Sonogashira reaction: a booming methodology in synthetic organic chemistry. Chemical Reviews, 107, 874–922.
58.
Prepared according to a reported procedure starting from but-1-yne, see: ZweifelG, LewisW., (1978) Stereoselective syntheses of ((E)- and (Z)-1-halo-1-alkenyl)silanes from alkynes. The Journal of Organic Chemistry, 43, 2739–2744.
59.
GreeneTW, WutsPGM. (1991) Protective Groups in Organic Synthesis, 2nd edition, J. Wiley & Sons.
60.
KocienskiP. J. (1994) Protecting Groups, Georg Thieme Verlag.
61.
TrostBM, BallZT, JögeT. (2002) A chemoselective reduction of alkynes to (E)-alkenes. Journal of the American Chemical Society, 124, 7922–7923;
62.
LacombeF, RadkowskiK, SeidelG, FürstnerA. (2004) (E)-Cycloalkenes and (E, E)-cycloalkadienes by ring closing diyne- or enyne-yne metathesis/semi-reduction. Tetrahedron, 60, 7315–7324;
63.
KleinbeckF, CarreiraEM. (2009) Total synthesis of bafilomycin A1. Angewandte Chemie International Edition, 48, 578–581;
64.
BressyC, BargiggiaF, GuyonnetM, ArseniyadisS, CossyJ., (2009) One-Pot hydrosilylation-RCM-protodesilylation: application to the synthesis of ω-alkenyl α,β-unsaturated lactones. Synlett, 565–568;
65.
BressyC, VorsJP, HillebrandS, ArseniyadisS, CossyJ., (2008) Asymmetric total synthesis of the immunosuppressant (-)-pironetin. Angewandte Chemie International Edition, 47, 10137–10140.
66.
StefanE, TaylorRE. (2012) Stereoselective synthesis of the C9-C19 fragment of lyngbyaloside B and C via ether transfer. Organic Letters, 14, 3490–3493.
67.
LiuK, TaylorRE, KartikaR., (2006) Electrophile-induced ether transfer: a new approach to polyketide structural units. Organic Letters, 8, 5393-5395. For applications of the ether transfer, see:
68.
KartikaR, GruffiTR, TaylorRE. (2008) Concise enantioselective total synthesis of neopeltolide macrolactone highlighted by ether transfer. Organic Letters, 10, 5047–5050;
69.
KartikaR, TaylorRE. (2007) Electrophile-induced ether transfer: stereoselective synthesis of 2,4,6-trisubstituted tetrahydropyrans. Angewandte Chemie International Edition, 46, 6874–6877;
70.
KartikaR, TaylorRE. (2007) Electrophile-induced ether transfer: an expedient route to 2-cyano-tetrahydropyrans. Heterocycles, 74, 447–459;
71.
LiuK, AricoJW, TaylorRE. (2010) Application of stereoselective ether transfer to the synthesis of isotactic polyethers. The Journal of Organic Chemistry, 75, 3953–3975;
72.
KartikaR, FreinJD, TaylorRE. (2008) Electrophilone-induced ether transfer: stereoselective synthesis of 2,6-disubstituted-3,4-dihydropyrans. The Journal of Organic Chemistry, 73, 5592–5594.