Subscribe to RSS
DOI: 10.1055/s-0031-1289529
First Total Syntheses of (3R,5R)-Sonnerlactone and (3R,5S)-Sonnerlactone
Publication History
Publication Date:
19 October 2011 (online)
Abstract
First total syntheses of the macrocyclic natural products (3R,5R)-sonnerlactone and (3R,5S)-sonnerlactone, two new metabolites isolated from the endophytic fungus strain Zh6-B1, have been accomplished in eleven steps with 22% overall yield starting from enantiomerically pure (R)-propylene oxide prepared by hydrolytic kinetic resolution. Other key steps are Sharpless epoxidation, reductive elimination of iodo epoxide, and ring-closing-metathesis reaction for the construction of the macrolactone.
Key words
sonnerlactone - antiproliferative - Jacobsen’s hydrolytic kinetic resolution - Sharpless asymmetric epoxidation - ring-closing metathesis
- Supporting Information for this article is available online:
- Supporting Information
- 1
Li K.-K.Lu Y.-J.Song X.-H.She Z.-G.Wu X.-W.An L.-K.Ye C.-X.Lin Y.-C. Bioorg. Med. Chem. Lett. 2010, 20: 3326 - 2
Edrada RA.Heubes M.Brauers G.Wray V.Berg A.Gräfe U.Wohlfarth M.Mühlbacher J.Schaumann K.Sudarsono Bringmann G.Proksch P. J. Nat. Prod. 2002, 65: 1598 - 3
Sponga F.Cavaletti L.Lazzarini A.Borghi A.Ciciliato I.Losi D.Marinelli F. J. Biotechnol. 1999, 70: 65 - 4
Huang Z.Cai X.Shao C.She Z.Xia X.Chen Y.Yang J.Zhou S.Lin Y. Phytochemistry 2008, 69: 1604 -
5a
Bernan VS.Greenstein M.Maiese WM. Adv. Appl. Microbiol. 1997, 43: 57 -
5b
Fenical W.Jansen PR. Annu. Rev. Microbiol. 1994, 48: 559 -
6a
Gradillas A.Pérez-Castells J. Angew. Chem. Int. Ed. 2006, 45: 6086 -
6b
Deiters A.Martin SF. Chem. Rev. 2004, 104: 2199 -
6c
Grubbs RH. Tetrahedron 2004, 60: 7117 -
6d
Prunet J. Angew. Chem. Int. Ed. 2003, 42: 2826 -
6e
Love JA. In Handbook of MetathesisGrubbs RH. Wiley-VCH; Weinheim: 2003. p.296 -
6f
Trnka TM.Grubbs RH. Acc. Chem. Res. 2001, 34: 18 -
6g
Fürstner A. Angew. Chem. Int. Ed. 2000, 39: 3012 -
6h
Maier ME. Angew. Chem. Int. Ed. 2000, 39: 2073 -
6i
Grubbs RH.Chang S. Tetrahedron 1998, 54: 4413 -
6j
Armstrong SK. J. Chem. Soc., Perkin Trans. 1 1998, 371 -
6k
Gerlach K.Quitschalle M.Kalesse M. Tetrahedron Lett. 1999, 40: 3553 -
6l
Nevalainen M.Koskinen AMP. Angew. Chem. Int. Ed. 2001, 40: 4060 -
7a
Mohapatra DK.Reddy DP.Dash U.Yadav JS. Tetrahedron Lett. 2011, 52: 151 -
7b
Mohapatra DK.Somaiah R.Rao MM.Caijo F.Mauduit M.Yadav JS. Synlett 2010, 1223 -
7c
Mohapatra DK.Dash U.Naidu PR.Yadav JS. Synlett 2009, 2129 -
7d
Mohapatra DK.Sahoo G.Ramesh DK.Sastry GN. Tetrahedron Lett. 2009, 50: 5636 -
7e
Mohapatra DK.Rahman H.Pal R.Gurjar MK. Synlett 2008, 1801 -
7f
Mohapatra DK.Ramesh DK.Giardello MA.Chorghade MS.Gurjar MK.Grubbs RH. Tetrahedron Lett. 2007, 48: 2621 -
7g
Gurjar MK.Karmakar S.Mohapatra DK. Tetrahedron Lett. 2004, 45: 4525 -
7h
Gurjar MK.Nagaprasad R.Ramana CV.Karmakar S.Mohapatra DK. ARKIVOC 2005, (iii): 237 -
7i
Mohapatra DK.Yellol GS. ARKIVOC 2005, (iii): 144 -
7j
Mohapatra DK.Durugkar KA. ARKIVOC 2004, (i): 146 -
7k
Mohapatra DK.Yellol GS. ARKIVOC 2003, (ix): 21 -
8a
Nielson LPC.Stevenson CP.Blackmond DG.Jacobsen EN. J. Am. Chem. Soc. 2004, 126: 1360 -
8b
Schaus SE.Brandes BD.Larrow JF.Tokunaga M.Hansen KB.Gould AE.Furrow ME.Jacobsen EN. J. Am. Chem. Soc. 2002, 124: 1307 - 9
Kumar P.Gupta P.Naidu SV. Chem. Eur. J. 2006, 12: 1397 - 10
Yu W.Mei Y.Hua Z.Jin Z. Org. Lett. 2004, 6: 3217 -
11a
Gao Y.Hanson RM.Klunder JM.Ko SY.Masamune H.Sharpless KB. J. Am. Chem. Soc. 1987, 109: 5765 -
11b
Coussens LM.Werb Z. Nature (London) 2002, 420: 860 - 12
Rao AVR.Reddy ER.Joshi BV.Yadav JS. Tetrahedron Lett. 1987, 28: 6497 - 15
Mitsunobu O. Synthesis 1981, 1 - 16
Subramanian LR.Hanack M.Chang LWK.Imhoff MA.Schleyer P.Effenberger F.Kurtz W.Stang PJ.Dueber TE. J. Org. Chem. 1976, 41: 4099 -
17a
Luo F.-T.Wang R.-T. Tetrahedron Lett. 1991, 32: 7703 -
17b
Dushin RG.Danishefsky SJ. J. Am. Chem. Soc. 1992, 114: 655 -
17c
Kamisuki S.Takashi S.Mizushina Y.Hanashima S.Kuramochi K.Kobayashi S.Sakaguchi K.Nakata T.Sugawara F. Tetrahedron 2004, 60: 5695 - 18
Bhattacharjee A.Sequil OR.De Brabander JK. Tetrahedron Lett. 2000, 41: 8069
References and Notes
Spectral and Analytical
Data of
8a
[α]D
²5 -103.5
(c 2.0, CHCl3). IR (neat): ν = 3433,
2934, 1415, 1153, 1097, 1034, 925, 850. cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.72
(m, 1 H, CH=CH2),
5.20 (m, 2 H, CH=CH
2),
4.58 (ABq, J = 37.8,
6.6 Hz, 2 H, OCH
2OCH3), 4.28
(m, 1 H, CHOCH2OCH3),
4.04 (m, 1 H, CH3CHO), 3.39
(s, 3 H, OCH2OCH
3),
2.60 (br s,1 H, OH), 1.71-1.56 (m, 2 H, CHCH
2CH), 1.19 (d, J = 6.2 Hz,
3 H, CH3) ppm. ¹³C NMR (75
MHz, CDCl3): δ = 137.6,
116.8, 94.2, 72.3, 64.2, 55.6, 43.9, 23.3 ppm. ESI-MS: m/z = 183
C8H16O3Na [M + Na]+.
Spectral and Analytical
Data of 8b
[α]D
²5 +6.1
(c 1.0, CHCl3). IR (neat):
3432, 2933, 1644, 1153, 1098, 1034, 925, 767 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.67
(m, 1 H, CH=CH2),
5.28-5.16 (m, 2 H, CH=CH
2),
4.59 (ABq, J = 59.0,
6.8 Hz, 2 H, OCH
2OCH3), 4.24
(m, 1 H, CH3CHOSi), 3.98 (m,
1 H, CHOCH2OCH3), 3.39
(s, 3 H, CH2OCH
3),
1.78-1.57 (m, 2 H, CHCH
2CH), 1.18
(d, J = 6.0
Hz, 3 H, CH3) ppm. ¹³C NMR
(75 MHz, CDCl3): δ = 137.6,
116.7, 94.1, 75.1, 66.6, 55.6, 43.9, 23.3 ppm. ESI-MS: m/z (C8H16O3Na) =183 [M + Na]+.
Spectral and Analytical
Data of
7a
[α]D
²7 -59.6
(c 1.1, CHCl3). IR (neat):
3417, 2929, 1731, 1647, 1607, 1576, 1315, 1255, 1162, 1030, 967,
697 cm-¹. ¹H NMR
(300 MHz, CDCl3): δ = 11.71
(br s, 1 H, ArOH), 7.41-7.27 (m, 5 H, ArH), 6.37 (d, J = 2.2 Hz,
1 H, ArH), 6.34 (d, J = 2.2
Hz, 1 H, ArH), 5.89 (m, 1 H, CH=CH2),
5.65 (m, 1 H, CH=CH2),
5.45-5.16 (m, 4 H, CH=CH
2,
CH=CH
2), 5.07-4.91
(s, 2 H, ArOCH2), 5.04 (s, 2 H), 4.64 (m, 1 H, CH3CHOC=O), 4.50 (dd, J = 6.7, 2.8
Hz, 1 H, CHOCH2OCH3),
4.10 (m, 1 H, ArCH2), 3.64 (m, 1 H, ArCH2),
3.34 (s, 3 H, OCH3), 1.88-1.80 (dd, J = 6.6, 1.5
Hz, 2 H, OCHCH
2CHO), 1.40
(d, J = 6.2
Hz, 3 H, CH3) ppm.
¹³C
NMR (75 MHz, CDCl3): δ = 170.8,
165.5, 163.0, 144.5, 137.4, 137.6, 137.3, 128.6, 128.1, 127.5, 117.8,
117.6, 115.6, 111.35, 100.1, 93.7, 73.7, 69.9, 69.5, 55.6, 42.0,
40.3, 20.6 ppm. ESI-HRMS: calcd for C25H30O6Na [M + Na]+: 449.1940;
found: 449.1922.
Spectral and Analytical
Data of 7b
[α]D
²7 -23.12
(c 1.2, CHCl3). IR (neat):
2934, 1646, 1610, 1575, 1452, 1315, 1255, 1162, 1030, 966, 918,
695 cm-¹. ¹H NMR
(300 MHz, CDCl3): δ = 11.72
(br s, 1 H, ArOH), 7.40-7.31 (m, 5 H, ArH), 6.44 (d, J = 2.4 Hz,
1 H, ArH), 6.34 (d, J = 2.2
Hz, 1 H, ArH), 5.91 (m, 1 H, CH=CH2),
5.66 (m, 1 H, CH=CH2),
5.34-5.16 (m, 4 H, CH=CH
2,
CH=CH
2), 5.07-4.91
(m, 2 H, ArOCH2), 5.04 (s, 2 H, OCH
2OCH3), 4.64
(m, 1 H, CH3CHOC=O),
4.45 (dd, J = 6.7,
2.8 Hz, 1 H), 4.11 (m, 1 H), 3.65 (m, 1 H) 3.34 (s, 3 H, OCH2OCH
3), 1.88-1.81 (dd, J = 8.3, 1.5
Hz, 2 H, OCHCH
2CHO), 1.41
(d, J = 6.2
Hz, 3 H, CH3) ppm. ¹³C NMR
(75 MHz, CDCl3): δ = 170.5,
164.8, 163.0, 143.6, 137.7, 137.2, 136.1, 128.5, 128.1, 127.4, 126.9,
117.5, 115.5, 108.7, 100.5, 93.6, 74.5, 69.8, 55.5, 42.1, 40.2,
20.1 ppm. ESI-HRMS: m/z calcd
for C25H30O6Na [M + Na]+:
449.1940; found: 449.1927.
Spectral and Analytical
Data of 1
Mp 144-145 ˚C. [α]D
²0 +8.6
(c 1.0, EtOH). IR (KBr): 3504, 3423,
3179, 2941, 1657, 1609, 1458, 1391, 1318, 1264, 1207, 1165 cm-¹. ¹H
NMR (500 MHz, acetone-d
6): δ = 11.02 (br
s, 1 H), 9.29 (br s, 1 H) 6.28 (d, J = 2.1
Hz, 1 H), 6.24 (d, J = 2.1
Hz, 1 H), 4.96 (m, 1 H), 3.83 (m, 1 H), 3.72 (s, 1 H), 3.23 (dt, J = 13.4,
7.2 Hz, 1 H), 2.56 (ddd, J = 13.4,
8.2, 6.0 Hz, 1 H), 2.09 (m, 1 H), 2.01 (m, 2 H), 1.78 (m, 1 H),
1.53 (m, 1 H), 1.44 (d, J = 6.2
Hz, 3 H), 1.30 (m, 1 H) ppm. ¹³C NMR
(75 MHz, acetone-d
6): δ = 171.9,
163.4, 163.1, 149.5, 111.9, 106.2, 101.7, 73.2, 72.0, 45.9, 37.5,
37.0, 27.1, 21.5.ppm. ESI-MS: m/z = 267
C14H18O5 [M + H]+.
ESI-HRMS: m/z calcd for C14H18O5 [M + H]+:
267.1227; found: 267.1255.
Spectral and Analytical
Data of 2
Mp 154-155 ˚C. [α]D
²5 +55.0
(c 1.1, EtOH). IR (KBr): 3455, 2926,
1653, 1457, 1319, 1262, 1204, 1163, 1102 cm-¹. ¹H NMR
(300 MHz, acetone-d
6): δ = 11.6
(br s, 1 H), 9.25 (br s, 1 H), 6.31 (d, J = 2.2
Hz, 1 H), 6.24 (d, J = 2.2
Hz, 1 H), 5.40 (m, 1 H), 4.22 (m, 1 H), 3.39 (ddd, J = 12.6,
4.3, 3.9 Hz, 1 H), 2.40 (m, 1 H), 2.16 (m, 1 H), 1.70-1.91
(m, 3 H), 1.50 (m, 1 H), 1.45 (d, J = 6.4
Hz, 3 H), 1.31 (m, 1 H) ppm. ¹³C NMR
(75 MHz, acetone-d
6): δ = 172.6,
167.6, 164.6, 150.1, 113.1, 106.2, 102.8, 71.4, 67.8, 43.9, 38.2,
37.2, 29.5, 21.2 ppm. ESI-MS: m/z = 267
C14H18O5 [M + H]+.
ESI-HRMS: m/z calcd for C14H18O5 [M + H]+:
267.1227; found: 267.1206.