Coniferin and derivatives: A fast and easy synthesis via the aldehyde series using phase-transfer catalysis

Article abstract of DOI:10.1055/s-1998-2009

Coniferin was synthesised in good yields (56% starting from vanillin) under mild conditions. A one-pot coupling of the glucosidation and Wittig- type reactions led to coniferaldehyde tetra-O-acetylglucoside, easily reduced into tetra-O-acetylconiferin by sodium borohydride. Similar procedures were used for the synthesis of syringin and the glucoside of 4-coumaryl alcohol.

Full text of DOI:10.1055/s-1998-2009

February 1998
SYNTHESIS
157
Coniferin and Derivatives: a Fast and Easy Synthesis via the Aldehyde Series
Using Phase-Transfer Catalysis
Nicolas Daubresse,* Charlette Francesch, Farida Mhamdi, Christian Rolando*
Ecole Normale Supérieure, Département de Chimie, URA 1679 du CNRS, Processus d’Activation Moléculaire, 24 rue Lhomond,
75231 Paris Cedex 05, France
Fax + 33(1)44323465; E-mail: chr@roxane.ens.fr
Received 11 April 1997; revised 31 July 1997
dride/butyllithium, (1:1)27 ate-complexes affords mod-
erate yields of complicated mixtures. The partial reduc-
tion of the allylic double bond can only be avoided by use
of lithium borohydride in refluxing dimethoxyethane.28
The best synthesis to date consists of the reduction of an
acyl chloride group by sodium trimethoxyborohydride
under highly controlled conditions.18, 29
Abstract: Coniferin was synthesised in good yields (56% starting
from vanillin) under mild conditions. A one-pot coupling of the glu-
cosidation and Wittig-type reactions led to coniferaldehyde tetra-O-
acetylglucoside, easily reduced into tetra-O-acetylconiferin by
sodium borohydride. Similar procedures were used for the synthesis
of syringin and the glucoside of 4-coumaryl alcohol.
Key words: coniferin, lignin, phase transfer, syringin, Wittig
Cinnamyl alcohol glucosides 2a–c are of major
importance in the first steps of the lignification process of
plant cell walls.1–4 They are considered as the carrying
forms of cinnamyl alcohols 1a–c, from the inner part of
the cell to the cell wall. They may constitute reserves for
postponed lignification,5 and high concentrations (up to
3% d.w.) have been detected in several plants.6–8 Com-
pound 2b is an indicator of commitment of tracheid differ-
entiation in conifers,9 a precursor of podophyllotoxin,10
and also acts as a very efficient virulence gene inducer for
Agrobacterium tumefasciens.11
A new route is described here starting from simple alde-
hydes, via the protected glucosides of a,b-unsaturated
aldehydes 6 which are easily reduced into allylic alcohols
7, without deprotection of the glucosidic group
(Scheme).
Cinnamyl alcohols 1, released from 2 by a glucosidase,
immediately polymerise and are incorporated into lig-
nin;12 they are very sensitive to oxygen or any oxidising
reagent and are light-sensitive, and it is therefore impos-
sible to carry out any physiological study directly from 1.
Contrary to 1, the glucosides 2 are stable and have been
widely used for various series of radiolabelling
experiments.13–20 The scope of biochemical studies is
however limited by a poor access to substrates and ana-
logues. The existing syntheses of 2, developed for natural
and various 3H- or 13C-labelled compounds, are not satis-
factory.
Despite recent improvements in the synthesis of cin-
namyl alcohols 1 and aldehydes,21-23 direct glycosylation
of these compounds is almost no longer carried out, since
this is mainly limited to the monomethoxy b guaicyl and
dimethoxy c syringyl series, and gives only fair yields
(3424 and 50%25 in the case of 2b).
When starting from tetraacetyl glucosylated 4-hydroxy-
benzaldehydes, after malonic condensation or Wittig–
Horner reaction, the reduction of acid or ester groups by
lithium aluminium hydride26 or diisobutylaluminium hy- Scheme. Synthesis of coniferin 2b
Table 1. Structure of Cinnamyl Alcohol 1 and Corresponding Glucosides 2
X
R1
R2
Compound Name
1a
1b
1c
2a
2b
2c
H
H
H
H
H
H
OMe
H
H
Coumaryl Alcohol
Coniferyl Alcohol
Sinapyl Alcohol
Coumaryl Alcohol Glycoside
Coniferin
OMe
OMe
H
glucosyl
glucosyl OMe
glucosyl OMe
OMe
Syringin

158
Papers
SYNTHESIS
corded on a Bruker AM250 spectrometer. Melting points were
determined using a Büchi 510 apparatus. (1,3-Dioxolan-2-yl)methyl-
triphenylphosphonium bromide (4) was prepared as previously
described.22,41 Acetobromoglucose 3 was prepared by a standard
procedure from glucose pentaacetate and 35% HBr in glacial HOAc.
CH2Cl2 was distilled over CaCl2, EtOAc was distilled over K2CO3.
Silica gel 60254 mesh from Merck Co. was used for chromatography
columns, and the products were eluted under 2 atm with a CH2Cl2/
EtOAc (85:15) mixture unless otherwise specified.
We have recently described a very efficient procedure for
the vinylogation of aldehydes with 1,3-dioxolan-2-ylmeth-
yltriphenylphosphonium salt 4 by the use of phase-transfer
conditions in a new synthesis of cinnamyl alcohols 1 from
acetylated 4-hydroxybenzaldehydes.22 Similar results were
obtained when starting from tetra-O-acetyl glucosides of
4-hydroxybenzaldehydes. Con-sidering that those condi-
tions for the Wittig reaction with 4 were quite similar to the
conditions of glucosylation via the commonly used
Koenigs–Knorr Method,30–35 we have combined the two
4-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyloxy)benzaldehyde (8a):
Acetobromoglucose 3 (8.22 g, 20 mmol) was dissolved in CH2Cl2
steps in a one-pot process. The phenol was first mixed with (100 mL) with TDA-1 (6.46 g, 20 mmol) and 4-hydroxybenzalde-
hyde (3.66 g, 30 mmol) and sat. aq K2CO3 (100 mL) were added. The
emulsion which contained a white precipitate was stirred at 39 °C for
72 h. After filtration and addition of H2O (150 mL), the aqueous layer
was separated and extracted with CH2Cl2 (2 ´ 150 mL). Combined
acetobromoglucose 3 in slight excess and TDA-1 {tris[2-
(2-methoxyethoxy)ethyl]amine}36 in a refluxing emulsion
of dichloromethane and saturated aqueous potassium car-
bonate solution. Addition of phosphonium salt 4 in moder-
ate excess (4 is hydrolysed with a 4 h half-reaction time in
this medium) led to total transformation of 4-hydroxy-
benzaldehyde glucosides 8 into a,b-unsaturated 1,3-diox-
olanes 5. Yields (79% with vanillin, 86% with syring-
aldehyde) were far better than those obtained in two sepa-
rate steps (5 can be crystallised from absolute ethanol in
the reaction mixture but better yields were obtained by
purification by chromatography).
organic layers were washed with aq NaOH (100 mL, 0.5%), H2O
(100 mL), aq HCl (100 mL, 2%) and H2O (100 mL), then dried
(MgSO4) and concentrated. Purification by chromatography yielded
8a (2.2 g, 24%) as a white solid; mp 143 °C.
1H NMR (CDCl3): d = 1.98 (s, 3 H, CH3CO), 1.99 (s, 6 H, CH3CO),
2.00 (s, 3 H, CH3CO), 3.87 (ddd, 1 H, H5, J = 10.0, 5.5, 2.5 Hz), 4.10
(dd, 1 H, H6a, J = 12.5, 2.5 Hz), 4.22 (dd, 1 H, H6b, J = 12.5, 5.5
Hz), 5.18–5.08 (m, 2 H, H3, H4), 5.24–5.30 (m, 2 H, H1, H2), 7.04
(d, 2 H, Har2,6, J = 8.7 Hz), 7.79 (d, 2 H, Har3,5, J = 8.7 Hz), 9.80 (s,
1 H, CHO).
C21H24O11
calc.
found
C
55.75
55.71
H
5.35
5.33.
In the case of 4-hydroxybenzaldehyde, the one-pot
method could not be used. This reagent was not nucleo-
philic enough and kinetic competition favoured the for-
mation of tetra-O-acetylglucal. 4-Hydroxybenzaldehyde
was thus used in excess relative to 3 and the glucoside of
4-hydroxybenzaldehyde 8a was purified prior to the Wit-
tig reaction.
2-{2-[4-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyloxy)-
phenyl]ethenyl}-1,3-dioxolane (5a):
Compound 8a (3.4 g, 7.5 mmol) was dissolved in CH2Cl2 (75 mL)
with TDA-l (2.43 g, 7.5 mmol) and 4 (3.92 g, 9.2 mmol) and sat. aq
K2CO3 (75 mL) was added. The emulsion was warmed to reflux and
stirred for 15 h. After addition of water (100 mL), the aqueous layer
was extracted with CH2Cl2 (2 ´ 100 mL). Combined organic layers
were washed with H2O (50 mL), aq HCl (50 mL, 2%) and H2O
(50 mL), dried (MgSO4) and concentrated. Purification by chromato-
graphy yielded 5a (1.7 g, 43.5%) as a white powder.1H NMR spectra
indicate a 70:30 Z/E ratio.
The protecting dioxolane group was not opened under
these conditions (contrary to what we observed when the
phosphonium ylide was generated with a strong base
such as BuLi). Z/E ratios are between 60:40 and 90:10,
depending on the reaction temperature and the series con-
sidered. After treatment with catalytic amounts of bro-
mine,37 followed by acidic treatment, we obtained pure
(E)-a,b-unsaturated aldehydes 6. The final reduction was
performed with sodium borohydride.22, 23 The protecting
acetyl groups of 7 were removed by transesterification
with catalytic sodium methoxide followed by neutralisa-
tion with acidic resin leading to pure 2.19, 29
C25H30O12
calc.
found
C
57.47
57.50
H
5.79
5.65.
2-{2-[3-Methoxy-4-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl-
oxy)phenyl]ethenyl}-1,3-dioxolane (5b):
Acetobromoglucose 3 (12.3 g, 30 mmol) was dissolved in CH2Cl2
(100 mL) with TDA-1 (6.46 g, 20 mmol) and vanillin (3.04 g,
20 mmol). Sat. aq K2CO3 (100 mL) was added. The emulsion which
contained a white precipitate was stirred at 40°C for 15 h. After cool-
ing at r.t., phosphonium salt 4 (17.16 g, 40 mmol) was added and the
emulsion was heated again for 24 h. After filtration and addition of
H2O (150 mL), the aqueous and organic layers were separated; the
aqueous layer was extracted with CH2Cl2 (2 ´ 150 mL). Combined
organic layers were washed with aq NaOH (100 mL, 2.5%), H2O
(100 mL; maintained at pH 7 by addition of aq 10% HCl) and H2O
(100 mL), dried (MgSO4) and concentrated. Purification by chroma-
tography yielded 5b as a white solid (8.8 g, 79%). NMR spectra indi-
cate a 60:40 Z/E ratio.
Coniferin 2b and analogues 2a and c can be synthesised
now routinely, in four steps starting from commercially
available compounds, on a several gram scale. Syntheses
of labelled derivatives are also shortened. This new syn-
thesis actually allows the labelling on carbon (14C for
radioactive studies or 13C for solid NMR observation of
lignin), or hydrogen (3H or 2H) on the ring, the a-position
of the propyl chain or the methyl groups, when starting
from labelled benzaldehydes.18,26,38,39 Reduction with
C26H32O13
calc.
found
C
56.52
56.58
H
5.84
5.98.
2
sodium borodeuteride affords H-labelled compounds on
2
2-{2-[3,5-Dimethoxy-4-(2,3,4,6-tetra-O-acetyl)-b-D-glucopyrano-
syloxy)phenyl]ethenyl}-1,3-dioxolane (5c):
Same procedure as described for 5b, starting from syringaldehyde
(3.64 g, 20 mmol) with a smaller amount of acetobromoglucose 3
(26 mmol) and phosphonium salt 4 (30 mmol).1H NMR spectra indi-
cate a 70:30 Z/E ratio. Yield: 10.0 g (86%).
the g-position and use of H2O as a medium during the
Wittig reaction leads to compounds deuterated on the b-
position.40
Microanalyses were performed by the Service Central d’analyse du
Centre National de la Recherche Scientifique, Vernaison, France. MS
experiments (Chemical Ionisation,1NH3) were carried out on a Ner-
mag R10–10C mass spectrometer.1H and 13C NMR spectra were re-
C27H34O14
calc.
found
C
5.67
55.61
H
5.88
5.94.

February 1998
SYNTHESIS
159
(E)-3-[3-Methoxy-4-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl-
oxy)phenyl]prop-2-enal (6b); Typical Procedure:
(E)-3-[4-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyloxy)phenyl]
prop-2-en-1-ol (7a):
The E/Z mixture of 5b (8.8 g, 16 mmol) was dissolved in CCl4 cf 7b. Yield: 1.85 g from 2 g 6a, 92%; mp 135 °C.
(200 mL). The solution was cooled to 0 °C and a solution of Br2 1H NMR (CDCl3): d= 2.05 (s, 3 H, CH3CO), 2.06 (s, 3 H, CH3CO), 2.08
(100 mg, 0.63 mmol) in CCl4 (10 mL) was added. The solution was (s, 3 H, CH3CO), 2.12 (s, 3 H, CH3CO), 3.86 (ddd, 1 H, H5, J = 9.7, 5.4,
stirred at 20°C for 1 h. To this were added H2O (10 mL) and HOAc 2.6 Hz), 4.15 (dd, 1 H, H6a, J = 12.2, 2.6 Hz), 4.29 (dd, 1 H, H6b,
(10 mL) and stirring was maintained for 10 h at r.t. The solution was J = 12.2, 5.4 Hz), 4.32 (br d, 2 H, CHCH2OH, J = 5.8 Hz), 5.4 (d, 1 H,
diluted with CH2Cl2 (150 mL) and aq KOH (9.5 g of KOH in 150 mL H1, J = 7.5 Hz), 5.12–5.33 (m, 3 H, H2, H3, H4), 6.28 (dt, 1 H,
H2O) was added. The aqueous layer was extracted with CH2Cl2 CHCH2OH, J = 15.8, 5.8 Hz), 6.58 (br d, 1H,ArCH, J = 15.8 Hz), 6.94
(2 ´ 50 mL), combined organic layers were washed with aq Na2S2O3 (d, 2 H, Har2,6, J = 8.7 Hz), 7.34 (d, 2 H, Har3,5, J = 8.7 Hz).
(50 mg, 50 mL), aq NaHCO3 (100 mL semi-sat. aq NaHCO3) and
C23H28O11
calc.
found
C
57.50
57.30
H
5.87
5.76.
H2O (100 mL), dried (MgSO4) and concentrated. The syrup was mix-
ed for 1 h with refluxing Et2O (50 mL). After 24 h at 4°C 6.18 g
(76%) of white crystals were collected; mp 159–160.5 °C (lit.:
160°C).25
(E)-3-[3,5-Dimethoxy-4-(2,3,4,6-tetra-O-acetyl-b-D-glucopyrano-
syloxy)phenyl]prop-2-en-1-ol (7c):
cf 7b. Yield: 5.1 g from 5.37 g 6c, 95%; mp 157–l59 °C.
1H NMR (CDCl3): d = 2.04 (s, 9 H, CH3CO), 2.05 (s, 3 H, CH3CO),
3.72 (ddd, 1 H, H5, J = 9.8, 4.9, 2.6 Hz), 3.86 (s, 6 H, CH3O), 4.11
(dd, 1 H, H6a, J = 12.2, 2.6 Hz), 4.25 (dd, 1 H, H6b, J = 12.2,
4.9 Hz), 4.33 (br d, 2 H, CHCH2OH, J = 5 Hz), 5.08 (d, 1 H, H1,
J = 7.1 Hz), 5.26–5.37 (m, 3 H, H2, H3, H4), 6.28 (dt, 1 H,
CHCH2OH, J = 15.7, 5 Hz), 6.54 (br d, 1 H, ArCH, J = 15.7 Hz),
6.60 (s, 2 H, Har).
1H NMR (CDCl3): d = 2.04 (s, 3 H, CH3CO), 2.06 (s,3 H, CH3CO),
2.11 (s, 3 H, CH3CO), 2.16 (s, 3 H, CH3CO), 3.82 (m, 1 H, H5), 3.86
(s, 3 H, CH3O), 4.19 (dd, 1 H, H6b), 4.20 (dd, 1 H, H6a), 5.04–5.32
(m, 4 H, H1, H2, H3, H4), 6.66 (dd, 1 H, CHCHO, J = 15, 7 Hz),
7.20–7.10 (m, 3 H, Har), 7.45 (d, 1 H, ArCH, J = 15 Hz), 9.70 (d, 1 H,
CHO, J = 7 Hz).
C24H28O12
calc.
C
56.69
56.61
H
5.55
found
5.48.
C25H32O13
calc.
C
5.55
H
5.97
found
55.52
5.98.
(E)-3-[4-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyloxy)phenyl]
(E)-3-(4-b-D-Glucopyranosyloxy-3-methoxyphenyl)prop-2-en-1-
ol (2b) (Coniferin); Typical Procedure:
prop-2-enal (6a):
cf 6b; yield: pure E-isomer, 1.02 g from 1.33 g 5a, 84%; mp 149–
Compound 7b (3.5 g, 6.82 mmol) was dissolved in anhyd MeOH
(150 mL), under N2, and NaOMe in MeOH (Na0: 10 mg, 10 mL) was
added at 0°C. The solution was stirred for 3 h (TLC checking recom-
mended). Acidic resin (Amberlyst, 1 g), washed with distilled H2O
(3 ´ 50 mL) and MeOH (4 ´ 50 mL), was added, and the solution was
filtered and concentrated under vacuum at r.t., leading to a light-white
powder: 2.4 g (100%). Further purification was achieved by chroma-
tography (eluent: EtOAc/acetone/H2O 10:10:1). White crystals of
2b · 2 H2O were collected after concentration under vacuum at r.t.
(1.9 g, 79.1%); mp: 2b · 2H2O: 140–150°C; after drying at 60°C, un-
der vacuum: 181–181.5 °C (lit.: 185 °C).25
150°C.
1H NMR (CDCl3): d = 2.04 (s, 6 H, CH3CO), 2.06 (s, 6 H, CH3CO),
3.95–3.87 (m, 1 H, H5), 4.15 (dd, 1 H, H6a, J = 12.5, 2.5 Hz), 4.22
(dd, 1 H, H6b, J = 12.5, 5.5 Hz), 5.10–5.33 (m, 4 H, H1, H2, H3, H4),
6.66 (dd, 1 H, CHCHO, J = 15, 7 Hz), 7.05 (d, 2 H, Har2,6, J = 7 Hz),
7.45 (d, 1 H, ArCH, J = 15 Hz), 7.54 (d, 2 H, Har3,5, J = 7 Hz), 9.65
(d, 1 H, CHO, J = 7 Hz).
C23H26O11
calc.
found
C
57.74
57.62
H
5.47
5.31.
1H NMR (CD3OD): d = 3.27–3.43 (m, 4 H, H2,3,4,5), 3.58 (m, 1 H,
H6a), 3.75 (m, 1 H, H6b), 3.77 (s, 3 H, CH3O), 4.08 (d, 2 H,
ArCHCHCH2, J = 5.6 Hz), 4.86 (d, 1 H, H1, J = 7.0 Hz), 7.04 (d,
1 H, Har2, J = 2 Hz), 6.25 (dt, 1 H, ArCHCH, J = 15.9, 5.6 Hz), 6.54
(d, 1 H, ArCHCH, J = 15.9 Hz), 6.87 (dd, 1 H, Har6, J = 8.2, 2 Hz),
7.01 (d, 1 H, Har5, J = 8.2 Hz).
(E)-3-[3,5-Dimethoxy-4-(2,3,4,6-tetra-O-acetyl-b-D-glucopyrano-
syloxy)phenyl]prop-2-enal (6c):
cf 6b; yield: p4ure E-isomer, 7.3 g from 9.5 g 5c, 82%; mp 172–173 °C
(lit.: 182°C).42
1H NMR (CDCl3): d = 2.04 (s, 12 H, CH3CO), 3.82 (ddd, 1 H, H5),
3.86 (s, 6 H, CH3O), 4.07–4.15 (dd, 1 H, H6a), 4.22–4.28 (dd, 1 H,
H6b), 5.18 (d, 1 H, H1), 5.22–5.33 (m, 3 H, H2, H3, H4), 6.66 (dd,
1H, CHCHO, J = 15, 7 Hz), 6.79 (s, 2 H, Har), 7.39 (d, 1 H, ArCH,
J = 15 Hz), 9.7 (d, 1 H, CHO, J = 7 Hz).
C16H22O8 · 2H2O calc.
found
C
50.79
50.68
H
6.92
6.85.
(E)-3-(4-b-D-Glucopyranosyloxyphenyl)prop-2-en-1-ol (2a) (Glu-
coside of 4-Coumaryl Alcohol):
C25H30O13
calc.
found
C
55.76
55.82
H
5.61
5.62.
cf 2b; yield: 1.01 g from 1.85 g 7a, 100%; mp 178–180°C, after
drying under vacuum at 60°C (lit.: 180–182°C).26
(E)-3-[3-Methoxy-4-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl-
oxy)phenyl]prop-2-en-1-ol (7b); Typical Procedure:
1H NMR (CD3OD) d = 3.26–3.45 (m, 4 H, H2,3,4,5), 3.60 (m, 1 H,
H6a), 3.74 (m, 1 H, H6b), 4.09 (d, 2 H, ArCHCHCH2, J = 5.8 Hz),
4.86 (d, 1 H, H1, J = 7.0 Hz), 6.25 (dt, 1 H, ArCHCH, J = 15.9,
5.8 Hz), 6.56 (d, 1 H, ArCHCH, J = 15.9 Hz), 7.06 (d, 2 H, Har2,6,
J = 8.4 Hz), 7.36 (d, 2 H, Har3,5, J = 8.4 Hz).
NaBH4 (184 mg, 4.84 mmol) was added to a solution of 6b (5.08 g,
10 mmol) in THF (50 mL) and MeOH (30 mL) cooled at –10°C. Af-
ter stirring at 20°C for 1.5 h, aq HCl (20 mL, l%) was slowly added
to the mixture. Solvents were evaporated and the residue was imme-
diately extracted with CH2Cl2 (150, 150, 50 mL). Combined organic
layers were washed with H2O (150 mL), dried (MgSO4) and concen-
trated under vacuum. Yield: white crystals, 4.8 g (94%); mp 159–
160.5 °C (lit.: 132 °C).26
C15H20O7. H2O
calc.
found
C
54.54
54.47
H
6.71
6.71.
(E)-3-(3,5-Dimethoxy-4-b-D-glucopyranosyloxyphenyl)prop-2-
en-1-ol (2c) (Syriugin):
1H NMR (CDCl3): d = 2.04 (s, 6 H, CH3CO), 2.08 (s, 6 H, CH3CO),
3.76 (ddd, 1 H, H5, J = 9.7, 4.8, 2.3 Hz), 3.86 (s, 3 H, CH3O), 4.11 (dd,
1 H, H6a, J = 12.2, 2.3 Hz), 4.25 (dd, 1 H, H6b, J = 12.2, 4.8 Hz), 4.34
(d, 2 H, CHCH2OH, J = 5 Hz), 5.10 (d, 1 H, H1, J = 8 Hz), 5.26–5.33
(m, 3 H, H2, H3, H4), 6.30 (dt, 1 H, CHCH2OH, J = 15.8, 5), 6.54 (br
d, 1 H, ArCH, J = 15.8 Hz), 6.87 (dd, 1 H, Har6, J = 8.2, 1.5 Hz), 6.94
(d, 1 H, Har2, J = 1.5 Hz), 7.07 (d, 1 H, Har5, J = 8.2 Hz).
cf 2b; yield: 1.01g, 100% from 2 g 7c; mp 191–191.5 °C (lit.:
191 °C).42
1H NMR (DMSO d6): d = 3.00–3.25 (m, 4 H, H2, H3, H4, H5), 3.4
(m, 1 H, H6a), 3.58 (m, 1 H, H6b), 3.74 (s, 6 H, CH3O), 4.10 (d, 2 H,
ArCHCHCH2, J = 4.5 Hz), 4.90 (d, 1 H, H1, J = 6.7 Hz), 6.30 (dt,
1 H, ArCHCH, J = 15.9, 4.9 Hz), 6.45 (d, 1 H, ArCHCH, J = 15,
9 Hz), 6.71 (s, 2 H, Har2,6 Hz).
C17H24O9 · H2O
alc.
found
C
52.30
51.75
H
6.71
6.54.
C24H30O12
calc.
found
C
56.47
56.43
H
5.92
5.78.

160
Papers
Table 2. 13C NMR Chemical Shifts
SYNTHESIS
Entry
1
2
3
4
5
6
7
8
9
8a
6a
6b
6c
7a
7b
7c
2a
2b
2c
129.1
129.1
130.4
130.6
128.4
128.1
133.7
131.4
133.9
133.0
116.7
117.4
122.3
105.7
117.0
120.0
103.7
116.4
121.0
104.8
131.7
130.1
148.5
137.0
127.6
145.7
134.0
127.1
147.9
134.2
162.1
158.7
150.8
152.3
156.3
150.6
152.9
157.2
151.1
153.1
170
170
170
170
170
170
170
20.5
20.6
20.6
20.6
20.6
20.6
20.6
119.3
119.2
118.1
2¢
111.6
110.3
111.6
3¢
56.1
56.3
55.9
56.2
57.0
56.7
Entry
a
b
g
1¢
4¢
5¢
6¢
8a
6a
6b
6c
7a
7b
7c
2a
2b
2c
190.6
152.5
152.0
152.3
128.4
130.4
130.4
129.7
131.6
130.6
98.0
98.6
100.0
100.8
99.0
100.7
101.2
100.8
102.9
103.0
71.0
71.0
71.0
71.9
71.1
71.1
71.7
76.6
75.1
74.6
72.3
72.1
72.1
72.9
72.0
72.5
73.0
78.4
78.4
77.6
68.1
68.2
68.4
68.3
66.2
68.3
68.4
70.0
71.6
70.3
72.5
72.4
72.5
71.9
72.7
71.9
71.9
76.8
78.1
76.9
61.8
61.8
61.8
62.2
61.7
61.9
62.2
61.1
62.7
61.2
127.7
127.9
128.4
132.1
133.5
128.7
128.0
129.2
128.9
193.4
193.4
193.4
63.6
63.5
63.3
62.4
64.0
61.8
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