A total synthesis of the styryllactone (+)-goniodiol from naphthalene

Article abstract of DOI:10.1071/CH02242

The cytotoxic natural product (+)-goniodiol (1) has been prepared in twelve steps from the enantiomerically pure cis-dihydrocatechol (2), which is readily obtained by microbial oxidation of naphthalene. Elaboration of compound (2) involves an initial oxid

Full text of DOI:10.1071/CH02242

CSIRO PUBLISHING
www.publish.csiro.au/journals/ajc
Aust. J. Chem. 2003, 56, 585–595
A Total Synthesis of the Styryllactone (+)-Goniodiol from Naphthalene∗
Martin G. Banwell,A,B Mark J. Coster,A Alison J. Edwards,A Ochitha P. Karunaratne,A
Jason A. Smith,A Lee L. WellingA and Anthony C. WillisA
AResearch School of Chemistry, Institute of Advanced Studies, The Australian National University,
Canberra 0200, Australia.
BAuthor to whom correspondence should be addressed (e-mail: mgb@rsc.anu.edu.au).
The cytotoxic natural product (+)-goniodiol (1) has been prepared in twelve steps from the enantiomerically pure
cis-dihydrocatechol (2), which is readily obtained by microbial oxidation of naphthalene. Elaboration of compound
(2) involves an initial oxidative cleavage to dialdehyde (7) followed by reduction to give diol (12). Conversion of
compound (12) into acetal (17) required, inter alia, selective oxidation of the benzylic alcohol moiety followed by a
metal-catalyzed decarbonylation of the resulting aldehyde. Allylation of compound (17) with allyltributylstannane
in the presence of lithium perchlorate gave a ca. 2.7 : 1 mixture of alcohols (18) and (19), each of which was
converted into the corresponding acrylate under standard conditions. Subjection of these ester derivatives to a ring-
closing metathesis (RCM) reaction with Grubbs’ first-generation catalyst gave the anticipated lactones (22) and
(23). Acid-catalyzed removal of the acetonide protecting group within compound (22) then afforded (+)-goniodiol
(1), while analogous deprotection of congener (23) afforded 6-epi-(+)-goniodiol (24).
Manuscript received: 21 November 2002.
Final version: 21 February 2003.
OH
Introduction
OH
OH
OH
The styryllactone(+)-goniodiol(1)(Diagram 1) wasfirstiso-
lated by Talapatra and coworkers[1] in 1985 from the leaves
and twigs of the Asian tree Goniothalamus sesquipedalis,
and again in 1991 by McLaughlin et al.[2] from ethanol
extracts of the stem bark of Goniothalamus giganteus
Hook f. & Thomas (Annonaceae). The latter group also
established that the compound exhibits significant cyto-
toxicity (IC50 1.22 × 10−1 µg mL−1) against the A-549
human lung tumour cell line whilst being essentially com-
pletely non-toxic (LC50 > 500 µg mL−1) in a brine shrimp
assay. The naturally occurring diacetate derivative of (+)-
goniodiol also shows some toxicity towards Aedes aegypti
larvae.[3] Such properties of this and other styryllactones
have prompted considerable effort directed towards the syn-
thesis of members of the class. The most popular target
has been (+)-goniodiol, at least in part because a num-
ber of its natural congeners can be obtained by simple
manipulations of this ‘parent system’.[4] The first synthe-
sis of the title compound was reported in 1992 by Honda
et al.,[5] who used readily available 2,3-O-isopropylidene-d-
glyceraldehyde as starting material. Two years later, Zhou[6]
described a synthesis starting with the Sharpless asymmetric
epoxidation of (E)-cinnamyl alcohol. The first of Vatele’s
three syntheses[7–9] was detailed in 1996 and employed
a monosaccharide-derived auxiliary to establish chirality
6
O
O
(2)
(1)
Diagram 1.
in the target molecule, whilst two related syntheses from
the same group used (R)-mandelic acid as starting material.
In 1997 Mukai and Hanaoka reported[10] the preparation of
compound (1) from the metal complex (+)-tricarbonyl[η6-o-
(trimethylsilyl)benzaldehyde] chromium(0), whilst in the
following year, Ley and Dixon[11] described a synthesis
from commercially available (S)-glycidol which involved
an anomeric oxygen-to-carbon rearrangement as the pivotal
step. Very recently, Lin et al.[12] described an enantio-
selective synthesis of (+)-goniodiol starting with asymmet-
ric dihydroxylation (AD) of 1-phenylbuta-1,3-diene, whilst a
US group exploited an asymmetric alkoxyallylboration–ring-
closing metathesis sequence to achieve the same target.[13]
Herein we report that (+)-goniodiol (1) can be prepared
from the enantiomerically pure ‘naphthalene diol’ (2),[14]
a
compound available in multi-gram quantities by means of
microbial dihydroxylation of naphthalene. The present work
∗Aspects of this work have been reported previously in communication form: M. G. Banwell, M. J. Coster, O. P. Karunaratne, J. A. Smith, J. Chem. Soc.,
Perkin Trans. 1 2002, 1622.
© CSIRO 2003
10.1071/CH02242
0004-9425/03/060585

586
M. G. Banwell et al.
thus provides the first application of this abundant metabolite
to the synthesis of natural products and serves to high-
light the extraordinary utility of such enzymatically derived
dihydrocatechols.[14,15]
excise the single superfluous carbon associated with the
starting material. Dialdehyde (4) could, in turn, be gener-
ated by oxidative cleavage of a suitably protected form of the
starting diol (2).
In initial attempts (Scheme 1) to implement the ideas
delineated in the retrosynthetic analysis, compound (2) was
converted into the previously reported[16] acetonide (5),
which was then subjected to cis-1,2-dihydroxylation under
the UpJohn conditions[17] to give a diastereoisomerically
pure and crystalline diol (6) (73%). Whilst the stereo-
chemical outcome of this reaction has not been rigorously
proven, the assignment of the illustrated configurations to
the newly introduced hydroxy groups within (6) follows by
analogy to related conversions observed in these and other
laboratories,[14,15] and involves cis-dihydroxylation from the
sterically less-hindered face of the alkene in precursor (5).
Oxidative cleavage of compound (6) could be effected with
sodium periodate in aqueous methanol at pH 7, and the
dialdehyde (7) thereby obtained in quantitative yield. Direct
oxidative cleavage of alkene (5) with OsO4/NaIO4 was less
efficient, giving product (7) in 69% yield. On the basis that
the aliphatic aldehyde moiety within compound (7) would
be more electrophilic than its aromatic counterpart, attempts
weremadetoselectivelyallylatetheformer.Whenacombina-
tion of allyltributylstannane and lithium perchlorate[18] was
employed for this purpose, and calcium hydride added in an
effort to convert any hydrated form of compound (7) into the
aldehyde itself, the crystalline allylation product (8) (43%)
was obtained as the only isolable product of reaction. The
structure of compound (8) was established by single-crystal
X-ray analysis (Fig. 2, Tables 1 and 2) and most likely arises
via a base-catalyzed intramolecular Claisen–Schmidt reac-
tion of dialdehyde (7) followed by allylation of the resulting
aldol at the carbonyl residue. In the absence of added calcium
Results and Discussion
Retrosynthetic analysis of target (1) (Fig. 1) suggests that the
lactone ring could be generated by ring-closing methathesis
of the acrylate (3) which should, in turn, be accessible by
a reaction sequence involving allylation of the aliphatic alde-
hyde within dialdehyde (4) and acrylation of the resulting
homoallylic alcohol as well as decarbonylation of the aro-
matic aldehyde moiety. The latter operation, which is not
often utilized in natural products synthesis, would serve to
OP
OP
RCM
(1)
O
O
P = OH protecting group
(3)
OP
oxidative
cleavage
OP
O
(2)
O
(4)
Fig. 1. Retrosynthetic analysis of (+)-goniodiol.
O
O
O
O
O
O
OsO4
NMO
NaIO4
2,2-DMP
(2)
p-TsOH
1
OH
O
OH
O
(5)
(6)
(7)
allylSnBu3, LiClO4
O
O
O
O
O
O
O
ϩ
O
HO
RO
HO
OH
(H2C=CHCO)2O,
Et3N, DMAP
(10) R=H
(11) R=COCHCH2
(9)
(8)
Scheme 1.

A Total Synthesis of the Styryllactone (+)-Goniodiol from Naphthalene
587
hydride, the allylation of compound (7) proceeded in the
expected manner and the homoallylic alcohol (9) was
obtained as the predominant reaction product (50%). Due to
the complexities of the NMR data, the lack of crystalline
material, and the lack of synthetic utility (see below) of
compound (9), the configuration at the new stereogenic cen-
tre within this product has not been determined. In an effort
to exploit hydroxyaldehyde (9) in the synthesis of target
(1) the acrylate derivative was sought. However, reaction
of compound (9) with acrylic anhydride in the presence
of 4-(N,N -dimethylamino)pyridine (DMAP) as an acylation
catalyst and using triethylamine as base afforded ester (11)
(22%; derived from lactol (10) which must be in equilib-
rium with hydroxyaldehyde (9)) as the only isolable product.
In a similar vein, attempts to decarbonylate compound (9)
using conditions successfully employed for the analogous
conversion of a related substrate (see below) were unsuc-
cessful, with acetonide group migration appearing to be
one of several processes taking place under the conditions
employed. Attempts to selectively mono-decarbonylate what
should be the more reactive aromatic aldehyde moiety within
dicarbonyl compound (7) were also unsuccessful.
C14
O3
C13
C7
C9
C6
C2
O1
C5
C4
C8
C10
C12
C15
C11
O15
O11
The early stages of the ultimately successful route to
(+)-goniodiol (1) are shown in Scheme 2 and began with
the reduction of dialdehyde (7) to the corresponding and pre-
viously reported[19] diol (12) (64% from (7)). The benzylic
alcohol moiety within this last compound was selectively
oxidized to the corresponding benzaldehyde (13) (70%)
using ‘precipitated active’ manganese dioxide as supplied
by Merck–Schuchardt. In order to prevent acetonide group
migration during the subsequent decarbonylation step the
hydroxy group within compound (13) was protected as the
corresponding acetate (14) (55%).
C16
C17
C18
Fig. 2. Anisotropic displacement ellipsoid plot of C16H20O4 (8) with
labelling of non-hydrogen atoms. Ellipsoids show 30% probability
levels. Hydrogen atoms are drawn as circles with small radii.
Several reagents were examined in connection with efforts
to effect decarbonylation of compound (14). Whilst read-
ily available Wilkinson’s complex [RhCl(PPh3)3] did affect
the desired reaction in refluxing xylene, stoichiometric quan-
tities of this ‘catalyst’ are required because the resulting
carbonyl–metal complex is stable and does not, there-
fore, ‘turn-over’.[20] Although such problems can sometimes
be overcome by adding diphenyl phosphorazidate,[20] this
proved ineffective in the present case. In principle, such dif-
ficulties could be avoided by using the cationic rhodium
complex bis[1, 3-bis(diphenylphosphino) propane]rhodium
tetrafluoroborate, [Rh(dppp)2]+ BF4−.[21] In order to exam-
ine such possibilities, this complex was prepared by
reaction of commercially available [Rh2Cl2(1,5-cod)2]
Table 1. Selected bond lengths (Å) for C16H20O4(8)
Atoms
Distance
Atoms
Distance
O(1)–C(2)
O(1)–C(12)
O(3)–C(2)
O(3)–C(4)
O(11)–C(11)
O(15)–C(15)
C(2)–C(13)
C(2)–C(14)
C(4)–C(5)
C(4)–C(12)
C(5)–C(6)
1.452(3)
1.441(2)
1.429(2)
1.431(3)
1.416(3)
1.447(3)
1.510(3)
1.502(3)
1.501(3)
1.542(3)
1.392(3)
C(5)–C(10)
C(6)–C(7)
C(7)–C(8)
1.386(4)
1.400(4)
1.383(4)
1.391(4)
1.390(3)
1.518(3)
1.558(3)
1.525(3)
1.531(3)
1.496(3)
1.321(4)
C(8)–C(9)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(15)
C(15)–C(16)
C(16)–C(17)
C(17)–C(18)
Table 2. Selected bond angles (degrees) for C16H20O4(8)
Atoms
Angle
Atoms
Angle
Atoms
Angle
C(2)–O(1)–C(12)
C(2)–O(3)–C(4)
O(1)–C(2)–O(3)
O(1)–C(2)–C(13)
O(3)–C(2)–C(13)
O(1)–C(2)–C(14)
O(3)–C(2)–C(14)
C(13)–C(2)–C(14)
O(3)–C(4)–C(5)
O(3)–C(4)–C(12)
C(5)–C(4)–C(12)
C(4)–C(5)–C(6)
109.70(14)
107.58(14)
104.76(15)
109.72(18)
111.27(19)
109.55(19)
108.31(17)
112.9(2)
109.49(17)
103.21(16)
105.35(18)
128.9(2)
C(4)–C(5)–C(10)
C(6)–C(5)–C(10)
C(5)–C(6)–C(7)
C(6)–C(7)–C(8)
C(7)–C(8)–C(9)
C(8)–C(9)–C(10)
C(5)–C(10)–C(9)
C(5)–C(10)–C(11)
C(9)–C(10)–C(11)
O(11)–C(11)–C(10)
O(11)–C(11)–C(12)
C(10)–C(11)–C(12)
110.25(18)
120.8(2)
118.1(3)
120.9(2)
120.9(3)
O(1)–C(12)–C(4)
O(1)–C(12)–C(11)
C(4)–C(12)–C(11)
O(1)–C(12)–C(15)
C(4)–C(12)–C(15)
C(11)–C(12)–C(15)
O(15)–C(15)–C(12)
O(15)–C(15)–C(16)
C(12)–C(15)–C(16)
C(15)–C(16)–C(17)
C(16)–C(17)–C(18)
103.91(16)
110.54(18)
104.55(17)
108.86(16)
115.86(18)
112.72(18)
109.47(18)
106.94(18)
113.69(18)
111.31(19)
126.1(3)
118.3(3)
121.0(2)
111.08(19)
127.9(2)
113.28(18)
113.81(18)
103.76(18)

588
M. G. Banwell et al.
O
O
O
[Rh(dppp)2]+
O
O
O
–
BF4
NaBH4
MnO2
(7)
OH
OR
OAc
OH
O
Ac2O,
DMAP
(13) R=H
(14) R=Ac
(15)
(12)
K2CO3,
MeOH
O
O
O
O
O
O
O
O
TPAP,
NMO
see
Table 1
ϩ
1
O
OH
HO
HO
(19)
(18)
(17)
(16)
Scheme 2.
Table 3. Selected bond lengths (Å) for
[Rh(dppp)2O2]+BF4−·2CH3COCH3
Atoms
Distance
Atoms
Distance
Rh(1)–P(1)
2.3445(15)
2.3763(16)
2.3873(17)
2.3360(15)
2.034(4)
2.047(4)
1.841(6)
1.839(6)
1.825(6)
P(2)–C(16)
P(2)–C(22)
P(3)–C(28)
P(3)–C(31)
P(3)–C(37)
P(4)–C(30)
P(4)–C(43)
P(4)–C(49)
O(1)–O(2)
1.841(6)
1.834(6)
1.840(5)
1.820(6)
1.826(6)
1.836(6)
1.828(6)
1.832(6)
1.426(5)
Rh(1)–P(2)
Rh(1)–P(3)
Rh(1)–P(4)
Rh(1)–O(1)
Rh(1)–O(2)
P(1)–C(1)
P(1)–C(4)
P(1)–C(10)
P(2)–C(3)
P3
O2
P4
Rh1
P1
O1
1.831(7)
P2
Table 4. Selected bond −angles (degrees) for
[Rh(dppp)2O2]+ BF4 ·2CH3COCH3
Atoms
Angle
Atoms
Angle
P(1)–Rh(1)–P(2)
P(1)–Rh(1)–P(3)
P(2)–Rh(1)–P(3) 170.52(5)
P(1)–Rh(1)–P(4)
P(2)–Rh(1)–P(4)
P(3)–Rh(1)–P(4)
P(1)–Rh(1)–O(1) 150.38(12) O(1)–Rh(1)–O(2)
P(2)–Rh(1)–O(1) 82.91(13)
90.93(6)
95.04(5)
P(3)–Rh(1)–O(1)
P(4)–Rh(1)–O(1) 109.54(12)
P(1)–Rh(1)–O(2) 110.11(11)
P(2)–Rh(1)–O(2)
P(3)–Rh(1)–O(2)
P(4)–Rh(1)–O(2) 149.95(11)
40.90(15)
88.28(12)
Fig. 3. Anisotropi−c displacement ellipsoid plot of the cation of
[Rh(dppp)2O2]+BF4 ·2CH3COCH3 (50% probability level) derived
from X-ray crystallographic data.
99.84(5)
95.11(5)
91.12(5)
87.12(12)
83.93(12)
(cod = cyclooctadiene) with silver tetrafluoroborate in the
presence of 1,3-bis(diphenylphosphino)propane (dppp).
However, this yellow-red compound readily incorporates
dioxygen into the coordination sphere to give the tan-
coloured complex [Rh(dppp)2O2]+BF4−,[22] in a process that
most likely takes place during attempts to effect recrystal-
lization from solvents which are not fully deoxygenated.
The structure of the latter complex, which has previ-
ously been characterized by NMR spectroscopic methods,
was confirmed by single-crystal X-ray analysis (Fig. 3,
Tables 3 and 4). In keeping with the behaviour of related
complexes,[23] heating a solution of [Rh(dppp)2O2]+BF−4 in
acetone under a nitrogen atmosphere overnight resulted in
regeneration of its deoxygenated counterpart, which read-
ily affects the desired conversion (14)→(15) (92% at 93%
conversion) in xylene at 140◦C. With due care, this decar-
bonylation reaction can be carried out on a 500 mg scale.
Hydrolysis of acetate (15) was accomplished with potas-
sium carbonate in methanol, and the resulting and previously
reported[6] alcohol (16)† (96%) was oxidized to aldehyde
(17)[6]† (62%) using the Ley–Griffith reagent.[26] The
allylation of compound (17) proved to be rather difficult to
† Whilst the triol corresponding to compound (16) has been prepared by asymmetric dihydroxylation (AD) of (Z)-cinnamyl alcohol, the enantiomeric excesses
observed are rather modest (ca. 70%).[24,25] The analogous dihydroxylation of (Z)-cinnamaldehyde does not appear to have been examined but AD of ethyl
(Z)-cinnamate gives the corresponding diol in 63% e.e. This material has been carried forward, using standard protection and reduction steps, to give ent-(17)
of the same enantiomeric purity.[25]

A Total Synthesis of the Styryllactone (+)-Goniodiol from Naphthalene
589
Table 5. Allylating agents employed in attempts to effect diastereoselective conversion of aldehyde (17) into
homoallylic alcohol (18)
Entry
Allylating agent
Literature
reference
Solvent
Temperature
(◦C)
Yield
(%)
Ratio of
(18)/(19)A
1
2
3
4
5
6
7
8
9
Allylmagnesium chloride
Allylmagnesium bromide
[27]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[18]
THF
0
0
−78
−78
18
52
47
13
ca. 85
ca. 50
89
76
64
60
70
3 : 4
2 : 3
1 : 1
1 : 2
1 : 1
3 : 11
1 : 3
2 : 3
4 : 3
8 : 3
ether
DCM
DCM
ether
ether
DCM
DCM
DCM
ether
Allyltrimethylsilane with BF3·OEt2
Allyltrimethylsilane with SnCl4
(−)-B-allyldiisopinocampheylborane
Diisopropyl (S,S)-tartrate allylboronate
Allyltributylstannane at 19 kbar
Allyltributylstannane with SnCl4
Allyltributylstannane with MgBr2·OEt2
Allyltributylstannane with LiClO4
−78
18
−78
−78
18
10
A Ratio determined by 1H NMR analysis.
M
(70% combined yield). These products could be separated
from one another by semi-preparative reverse-phase HPLC
techniquesandtheassignmentofstereochemistrywithineach
of them follows from their conversions into (+)-goniodiol (1)
and its C6-epimer (24), respectively.
H
O
O
O
O
O
H
O
si-face
(17a)
(17b)
re-face
Details associated with completion of the synthesis of tar-
get (1) from precursor (18) are shown in Scheme 3. Formation
of the required acrylate esters of compounds (18) and (19)
proved surprisingly difficult and the only useful conditions
for effecting reaction involved using acrylic anhydride in the
presence of DMAP. Replacing DMAP with the much-touted
scandium triflate[37] as an acylation catalyst failed to deliver
any esterified products.The esters (20) (47%) and (21) (52%)
were each subjected to reaction with (Cy3P)2Cl2Ru = CHPh
(Grubbs’ ‘first generation’ catalyst).[38] In keeping with the
behaviour of many other acrylates derived from homoallylic
alcohols,[39] compounds (20) and (21) readily engaged in
the anticipated RCM reaction thus affording the expected
pyranones (22) and (23) (79% and 73%), respectively. The
spectroscopic and physical data derived from product (22)
matched those obtained on authentic material,[11] which
was kindly provided by Professor S. V. Ley (Cambridge
University). The acetonide moieties associated with each
of compounds (22) and (23) could be removed by brief
treatment with aqueous acetic acid at 80◦C and, in this man-
ner (+)-goniodiol (1) (98%) and its C6-epimer (24) (85%)
were obtained. The NMR spectral data derived from com-
pound (1), prepared as described above, matched those of
authentic material.[6a,11] Furthermore, the specific rotation
of the natural and synthetic materials were in good agree-
ment (see Experimental section). The spectral data derived
from isomer (24) were also in full accord with the assigned
structure. Interestingly, the specific rotation of the C6-epimer
of (+)-goniodiol was negative {[α]D –47.4◦ (c 0.27)}.
allylation
allylation
H
HO
H
O
O
O
O
HO
O
O
O
O
HO
HO
syn-product (18)
anti-product (19)
Fig. 4. Chelation and non-chelation controlled allylation of alde-
hyde (17).
achieve with appropriate levels of diastereoselection. Indeed,
a wide range of reagents and conditions[18,27–35] were exam-
ined (Table 5) in an effort to obtain high yields of the required
syn-product (18), but in most instances (Entries 1–8) the
anti-isomer(19)predominated. Onthebasisthattherequired
re-face attack of the nucleophile at the aldehyde carbonyl
moiety within substrate (17) could be best effected under
conditions of chelation control[36] (Fig. 4), the combina-
tion of allyltributylstannane and magnesium bromide diethyl
etherate was examined and, in this case, a 4 : 3 mixture of
compounds (18) and (19) were obtained (Entry 9). This ratio
could be improved slightly by using lithium perchlorate as
the Lewis acid catalyst (Entry 10), and under such conditions
a ca. 8 : 3 mixture of products (18) and (19) was obtained
Conclusion
The work described here should serve to highlight the utility
of enantiomerically pure metabolite (2) as a starting material
for chemical synthesis. Since various heterocyclic and other
analogues of this compound are also available in optically
pure form[14,19] the reaction sequences detailed above could
be used to assemble analogues of (+)-goniodiol (1) which

590
M. G. Banwell et al.
O
O
O
O
1
RO
RO
(18) R=H
(20) R=COCH=CH2
(19) R=H
(21) R=COCH=CH2
(H2C=CHCO)2O,
DMAP
(H2C=CHCO)2O,
DMAP
(Cy3P)2Cl2Ru=CHPh
(Cy3P)2Cl2Ru=CHPh
OH
O
O
O
O
O
OH
6
6
AcOH/H2O
6
AcOH/H2O
(1)
O
O
O
O
O
(22)
(23)
(24)
Scheme 3.
vary, inter alia, in the nature and substitution patterns on the
aromatic ring. In addition, the manner in which the pyranone
moiety of target (1) is assembled should enable rapid con-
struction of analogues varying in the nature of substituents on
this ring. Overall, then, the route to (+)-goniodiol described
here should be amenable to the assembly of a range of ana-
logues, including other naturally occurring congeners, that
would be useful in developing a comprehensive structure–
activity relationship (SAR) profile of this interesting class of
cytotoxic agent.
performed by the Australian National University Microanalytical Ser-
vices Unit located within the Research School of Chemistry.Tetrahydro-
furan (THF) was distilled, under nitrogen, from sodium benzophenone
ketyl, dichloromethane from calcium hydride, and methanol from mag-
nesium methoxide. pH 7 Buffer solution was prepared by dissolving
potassium dihydrogenphosphate (85 g) and sodium hydroxide (14.5 g)
in water (950 mL).
Synthetic Studies
(3aS,4R,5R,9bR)-3a,4,5,9b-Tetrahydro-2,2-dimethylnaphtho[1,2-d]-
1,3-dioxole-4,5-diol (6)
A magnetically stirred solution of alkene (5)[16] (4.00 g, 16.9 mmol)
in acetone/water (150 mL of 2 : 1 v/v mixture) was treated with N-
methylmorpholine N-oxide (NMO) (3.96 g, 33.8 mmol, 2 mole equiv.)
followedbyOsO4 (1.7 mLofa2.5 wt%solutionint-butanol, 0.17mmol,
1 mol%). The resulting mixture was stirred at 18◦C for 16 h then treated
with Na2S2O3 (300 mL of a 10% w/v aqueous solution). After 0.25 h
the reaction mixture was extracted with diethyl ether (2 × 200 mL) and
then ethyl acetate (2 × 200 mL). The combined organic phases were
dried (Na2SO4), filtered through a 5 cm pad of TLC-grade silica gel
(ethyl acetate elution), and the filtrate concentrated under reduced pres-
sure to give a brown solid. Recrystallization (ethyl acetate/hexane) of
this material then gave the title diol (6) (3.41 g, 73%) as off-white nee-
dles, mp 145–146◦C, [α]D +19.7◦ (c 1.0) (Found: C, 65.9; H, 6.8%.
C13H16O4 requires C, 66.1; H, 6.8%). νmax (KBr)/cm−1 3480, 3178,
2988, 2891, 2868, 1454, 1376, 1242, 1221, 1091, 1064, 868, 771. δH
7.50–7.36 (4 H, complex m), 5.28 (1 H, d, J 6.7), 4.87 (1 H, dd, J 4.9
and 2.9), 4.53 (1 H, app. t, J 6.3), 4.04 (1 H, m), 2.93 (1 H, d, J 4.9), 2.78
(1 H, d, J 4.4), 1.48 (3 H, s), 1.44 (3 H, s). δC 136.2, 132.2, 129.7, 129.1,
128.8, 127.9, 109.3, 76.6, 74.6, 73.1, 69.8, 27.5, 25.2. Mass spectrum
(70 eV; EI) m/z 235 (1%, [M – H•]+), 221 (44, [M – CH•3]+), 178 (24),
161 (100), 133 (57), 131 (50), 115 (15), 103 (19), 91 (25), 77 (20).
Experimental
General
Melting points were recorded with a Kofler hot-stage apparatus and
are uncorrected. Unless otherwise indicated, proton (δH) and carbon
(δC) NMR spectra were recorded with a Varian Unity 300 or Varian
Gemini 300 spectrometer operating at 300 MHz for 1H and 75 MHz for
13C. All such spectra were recorded, unless indicated to the contrary,
in deuterochloroform (CDCl3) solution at 22◦C. The protonicities of
the carbon atoms observed in 13C NMR spectra were determined by
attached proton test (APT) experiments. Infrared spectra (νmax) were
recorded with either a Perkin-Elmer 983G infrared spectrophotometer
or a Perkin-Elmer 1800 Series FTIR instrument. Samples were ana-
lyzed either as thin films on NaCl plates (for liquids) or as KBr disks
(for solids). Low-resolution electron-impact mass spectra (m/z) were
recorded at 70 eV on either a VG Micromass 7070F mass spectrometer
or a JEOL AX-505H mass spectrometer. High-resolution mass spectra
were recorded with a VG Micromass 7070F instrument. HPLC separa-
tions were performed with an HP1090 HPLC instrument incorporating
a diode-array detector interfaced with HP ChemStation software and
on-board autosampler. An Alltech Apollo 5 µm C18 250 × 4.6 mm ana-
lytical column operating at 40◦C was employed. Peak detection was by
UV at 230 nm and 1 : 1 v/v MeCN/H2O was used as the eluting sol-
vent at a flow rate of 1 mL min−1. Optical rotations were determined
on a Perkin-Elmer 241 polarimeter at the sodium D line (589 nm) using
spectroscopic grade chloroform (unless otherwise specified) at 20◦C
and at the concentrations (c) (g/100 mL) indicated. Measurements were
carried out in a cell with a path length of 1 dm. Elemental analyses were
(4R-cis)-5-(2ꢀ-Formylphenyl)-2,2-dimethyl-1,3-dioxolane-
4-carboxaldehyde (7)
Method A. A magnetically stirred solution of diol (6) (1.18 g,
5.00 mmol) in methanol/1 M pH 7 buffer (180 mL of 5 : 1 v/v mixture)
was treated with water (ca. 10 mL) until homogeneous. The resulting
solution was cooled on an ice bath and NaIO4 (1.60 g, 7.5 mmol, 1.5
mole equiv.) was added in portions over 5 min. The resulting mixture

A Total Synthesis of the Styryllactone (+)-Goniodiol from Naphthalene
591
was removed from the ice bath and allowed to stir at 18◦C for 1 h and
was then diluted with water (200 mL) and extracted with diethyl ether
(4 × 100 mL). The combined organic phases were dried (MgSO4), fil-
tered, and concentrated under reduced pressure to give compound (7)
(1.18 g, 100%) as a clear, colourless oil. δH 10.04 (1 H, s), 9.02 (1 H, d,
J 2.8), 7.83 (2 H, m), 7.64 (1 H, m), 7.54 (1 H, m), 6.21 (1 H, d, J 7.9),
5.06 (1 H, dd, J 7.9 and 2.8), 1.77 (3 H, s), 1.58 (3 H, s). This material
was used, without purification, in the next step of the reaction sequence.
Method B. A magnetically stirred solution of alkene (5) (2.05 g,
10.1 mmol) in 1,2-dimethoxyethane (DME)/water (160 mL of 3 : 1 v/v
mixture) was treated with OsO4 (53 mL of a 2.5 wt% solution in
t-butanol, 1.02 mmol, 10 mol%). After 0.5 h, the reaction mixture was
treated, in portions over 5 min, with NaIO4 (6.55 g, 30.6 mmol, 3 mole
equiv.). The resulting mixture was stirred at 18◦C for 20 h then treated
with Na2S2O3 (30 mL of a 20% w/v aqueous solution). After 0.33 h the
reaction mixture was diluted with water (200 mL) and extracted with
diethyl ether (6 × 50 mL). The combined organic phases were dried
(MgSO4), filtered, and concentrated under reduced pressure to give
compound (7) (1.64 g, 69%) as a light-yellow and unstable oil. This
material was identical, as judged by 1H NMR analysis, with the material
obtained by Method A.
requires [M – CH•3]+, 261.1127). νmax (NaCl)/cm–1 3468, 2984, 1696,
1575, 1380, 1213, 1057, 881, 757. δH (major epimer) 10.03 (1 H, s),
7.93 (1 H, d, J 7.8), 7.80 (1 H, dd, J 7.5 and 1.3), 7.64 (1 H, dt, J 7.8
and 1.3), 7.52 (1 H, dt, J 7.5 and 0.9), 5.94 (1 H, d, J 7.3), 5.64 (1 H, m),
4.95 (1 H, m), 4.88 (1 H, m), 4.68 (1 H, dd, J 7.3 and 2.9), 3.02 (1 H, m),
2.06–1.85 (3 H, complex m), 1.68 (3 H, s), 1.53 (3 H, s). δC (major
epimer) 193.4 (CH), 138.8 (C), 135.3 (CH), 134.6 (CH), 134.0 (CH),
132.9 (C), 128.0 (2 × CH), 117.1 (CH2), 108.0 (C), 79.3 (CH), 76.4
(CH), 68.8 (CH), 39.6 (CH2), 27.0 (CH3), 24.7 (CH3). Mass spectrum
(70 eV; EI) m/z 261 (6%, [M – CH•3]+), 235 (6), 201 (17), 177 (99),
159 (39), 148 (55), 147 (73), 133 (74), 131 (72), 119 (90), 118 (100),
91 (68), 77 (39).
[3aS-(3aα,10bα)]-2,2-Dimethyl-4-(prop-2ꢀ-enyl)-3a,4,6,10b-
tetrahydro-1,3-dioxolo[4,5-d][2]benzoxepin-4(3aH)-one (11)
A magnetically stirred solution of alcohol (9) (37.4 mg, 0.135 mmol)
and DMAP (132 mg, 1.08 mmol) in anhydrous THF (0.5 mL) main-
tained at −20◦C under a nitrogen atmosphere was treated with acrylic
anhydride (5.2 mL of a 0.26 M solution in THF, 1.35 mmol, ca. 10
mole equiv.). The resulting solution was left at −20◦C for 16 h before
being quenched by the addition of water (10 mL) and was then extracted
with dichloromethane (3 × 5 mL). The combined organic portions were
dried (Na2SO4), filtered, and concentrated under reduced pressure to
give a yellow oil. Subjection of this material to flash chromatography
(silica, 5 : 95 → 3 : 7 v/v ethyl acetate/hexane gradient elution) pro-
vided, after concentration of the appropriate fractions (Rf 0.5 in 3 : 7
v/v ethyl acetate/hexane), the title compound (11) (9.8 mg, 22%) as a
clear, colourless oil. δH 7.46–7.35 (4 H, complex m), 7.37 (1 H, s), 6.53
(1 H, dd, J 17.3 and 1.5), 6.23 (1 H, dd, J 17.3 and 10.5), 5.94 (1 H, dd,
J 10.5 and 1.5), 5.70 (1 H, m), 5.14 (1 H, d, J 6.5), 5.06 (1 H, m), 4.96
(1 H, m), 4.26 (1 H, dd, J 6.5 and 1.0), 3.87 (1 H, ddd, J 8.8, 4.9 and
1.0), 2.47 (1 H, m), 2.23 (1 H, m), 1.67 (3 H, s), 1.50 (3 H, s).
(1ꢀR,3aR,8R,8aS)-8-Hydroxy-8a-(1ꢀ-hydroxybut-3ꢀ-en-1ꢀ-yl)-
2,2-dimethyl-8,8a-dihydro-8H-indeno[1,2-d]-1,3-dioxol-8-ol (8)
A magnetically stirred solution of dialdehyde (7) (47 mg, 0.20 mmol)
in diethyl ether (1 mL) was treated with calcium hydride (ca. 20 mg) for
30 min. The solvent was removed under reduced pressure and replaced
with lithium perchlorate (2 mL of a 5 M solution in ether) and the
resultant mixture was treated with allyltributylstannane (68 µL, 0.22
mmol). After 4 h at 18◦C the reaction mixture was quenched with pH
7 buffer solution (5 mL), diluted with water (20 mL), and extracted
with dichloromethane (3 × 5 mL). The combined organic phases were
washed with water (1 × 5 mL) and brine (1 × 5 mL) before being dried
(Na2SO4), filtered, and concentrated under reduced pressure to afford
a colourless oil. Subjection of this material to flash chromatography
(silica, 5 : 95 → 2 : 3 v/v ethyl acetate/hexane gradient elution) provided,
after concentration of the appropriate fractions (Rf 0.2 in 3 : 7 v/v ethyl
acetate/hexane), compound (8) (24 mg, 43%) •as white needles, mp 104–
106◦C, [α]D +86.5◦ (c 0.5) (Found: [M – CH3]+, 261.1126. C16H20O4
requires [M – CH• ]+, 261.1127). νmax (KBr)/cm−1 3401, 2988, 2934,
1641, 1381, 13703, 1243, 1212, 1027, 755. δH 7.50–7.37 (4 H, complex
m), 5.97 (1 H, m), 5.59 (1 H, s), 5.35 (1 H, d, J 4.0), 5.27–5.18 (2 H,
complex m), 4.08 (1 H, ddd, J 9.8, 6.3 and 2.5), 3.34 (1 H, d, J 4.0),
2.66 (1 H, d, J 6.3), 2.62 (1 H, m), 2.47 (1 H, m), 1.47 (3 H, s), 0.87
(3 H, s). δC 142.5, 141.8, 135.2, 129.9(9), 129.9(6), 125.8(5), 125.7(7),
118.3, 112.7, 94.0, 85.4, 81.8, 72.8, 36.6, 28.7, 28.5. Mass spectrum (70
eV; EI) m/z 261 (4%, [M – CH•3]+), 218 (30), 177 (49), 177 (49), 159
(100), 147 (43), 131 (75), 119 (34), 103 (35), 91 (43), 77 (25), 65 (19).
(4R-cis)-5-[2ꢀ-(Hydroxymethyl)phenyl]-2,2-dimethyl-
1,3-dioxolane-4-methanol (12)
A magnetically stirred and chilled (ice-bath) solution of dialdehyde (7)
(1.64 g, 7.00 mmol) in methanol (100 mL) was treated, in portions over
0.25 h, with sodium borohydride (1.10 g, 29.1 mmol, ca. 4 mole equiv.).
After 2 h the reaction mixture was quenched with brine (200 mL) and
the resulting mixture extracted with ethyl acetate (4 × 50 mL).The com-
bined organic layers were dried (MgSO4), filtered, and concentrated
under reduced pressure to give a brown oil. Subjection of this material
to flash chromatography (silica gel, ethyl acetate elution) gave, after
concentration of the appropriate fractions (Rf 0.4), the title diol (12)[19]
[1.06 g, 64% from (7)] as a viscous, light-brown oil, [α]D –80.3◦ (c 3.0)
(Found: [M – CH3• ]+, 223.0969. C13H18O4 requires [M – CH3• ]+,
223.0970). νmax (NaCl)/cm−1 3385, 2934, 1380, 1214, 1164, 1108,
1041, 752. δH 7.54 (1 H, br d, J 7.2), 7.33 (1 H, m), 7.26–7.21 (2 H,
complex m), 5.54 (1 H, d, J 7.0), 4.66 (1 H, br dd, J 12.0 and 4.3),
4.50–4.41 (2 H, complex m), 3.74 (1 H, br s), 3.24 (1 H, m), 3.00 (1 H,
m), 2.83 (1 H, br s), 1.61 (3 H, s), 1.47 (3 H, s). δC 137.5, 135.2, 129.4,
128.5, 128.2, 127.2, 108.6, 78.6, 75.3, 63.7, 62.5, 27.5, 24.9. Mass spec-
trum (70 eV; EI) m/z 223 (2%, [M – CH•3]+), 220 (12), 178 (8), 163
(6), 149 (14), 133 (21), 120 (100), 91 (31), 77 (13), 59 (65).
(4S-cis)-5-(2ꢀ-Formylphenyl)-2,2-dimethyl-(1ꢀ-hydroxybut-3ꢀ-en-
1ꢀ-yl)-1,3-dioxolane (9)
A magnetically stirred solution of dialdehyde (7) (234 mg, 1.00 mmol)
in lithium perchlorate (10 mL of a 5 M solution in ether) was treated with
allyltributylstannane (340 µL, 1.1 mmol) for 4 h at 18◦C. The reaction
mixture was then quenched with pH 7 buffer solution (50 mL), diluted
with water (200 mL), and extracted with dichloromethane (3 × 50 mL).
The combined organic phases were washed with water (1 × 20 mL) and
brine (1 × 20 mL) before being dried (Na2SO4), filtered, and concen-
trated under reduced pressure to afford a colourless oil. Subjection
of this material to flash chromatography (silica, 5 : 95 → 2 : 3 v/v
ethyl acetate/hexane elution) provided, after concentration of the appro-
priate fractions (Rf 0.1 in 1 : 4 v/v ethyl acetate/hexane), the title
aldehyde (9) (139 mg, 50%) as a clear, light-yellow oil containing ca.
10% starting dialdehyde (7) as impurity. This material could be puri-
fied by further flash chromatography (silica, 15 : 30 : 55 v/v/v diethyl
ether/dichloromethane/hexane elution) to provide an essentially pure
sample of the title aldehyde (9) (Rf 0.3) as a clear, colourless oil and
approximately a 10 : 1 mixture of epimers (as•judged by 13C NMR anal-
ysis), [α]D –184.0◦ (c 2.4) (Found: [M – CH3]+, 261.1126. C16H20O4
(4S-cis)-5-[2ꢀ-(Formyl)phenyl]-2,2-dimethyl-
1,3-dioxolane-4-methanol (13)
A solution of diol (12) (1.06 g, 4.47 mmol) in DME (45 mL) was
treated with ‘precipitated active’manganese dioxide (7.78 g, 89.5 mmol,
from MERCK-Schuchardt), and the resulting mixture was stirred at
18◦C for 16 h then filtered through a pad of Celite. The solids thus
retained were washed with DME (45 mL) and the combined filtrates
concentrated under reduced pressure to give an orange-red solid. Sub-
jection of this material to flash chromatography (silica, 3 : 7 ethyl
acetate/hexane elution) gave, after concentration of the appropriate
fractions (Rf 0.3 in 1 : 1 v/v ethyl acetate/hexane), the title hydroxy-
aldehyde (13) (746 mg, 70%) as a pale-yellow oil, [α]D –237.0◦
(c 6.5) (Found: [M – CH•3]+, 221.0813. C13H16O4 requires [M – CH•3]+,

592
M. G. Banwell et al.
221.0814). νmax (KBr)/cm−1 3467, 2987, 2936, 2744, 1694, 1600, 1575,
1381, 1213, 1166, 1044, 907, 868, 756. δH 10.04 (1 H, br s), 7.89 (1 H, d,
J 7.6), 7.81 (1 H, dd, J 7.5 and 1.5), 7.64 (1 H, br dt, J 7.6 and 1.5),
7.53 (1 H, br dt, J 7.5 and 1.1), 6.00 (1 H, br d, J 7.3), 4.84 (1 H, m),
3.02 (2 H, dd, J 6.5 and 5.3), 1.67 (3 H, s), 1.57 (1 H, t, J 6.5), 1.53 (3 H,
s). δC 193.2, 138.2, 135.1, 133.8, 132.8, 127.9, 127.1, 108.3, 77.9, 75.2,
62.7, 27.4, 24.7. Mass spectrum (ESI+) m/z 259 (100%, [M + Na]+),
235 (18, [M – H•]+), 219 (23).
Concentration of fractionA (Rf 0.25 in 1 : 4 v/v ethyl acetate/hexane)
gave the starting aldehyde (14) (48.6 mg, 7% recovery), which was
identical in all respects with an authentic sample.
Concentration of fraction B (Rf 0.4 in 1 : 4 v/v ethyl acetate/hexane)
gave the title acetate (15)[6] (509 mg, 92% at 93% conversion) as •a
white crystalline solid, mp 65–68◦C, [α]D −109◦ (c 1.1) (Found: M+
,
250.1205; C, 67.1; H, 7.2%. C14H18O4 requires M+•, 250.1205; C,
67.2; H, 7.3%). νmax (KBr)/cm−1 1735, 1376, 1237, 1212, 1087, 1033,
983, 752, 704. δH 7.38–7.30 (5 H, complex m), 5.32 (1 H, d, J 6.9),
4.56 (1 H, ddd, J 8.0, 6.9 and 4.4), 3.71 (1 H, dd, J 11.7 and 4.4), 3.61
(1 H, dd, J 11.7 and 8.0), 1.92 (3 H, s), 1.65 (3 H, s), 1.49 (3 H, s). δC
170.8, 136.3, 128.7, 128.5, 126.7, 109.5, 78.7, 76.5, 64.5, 27.6, 25.2,
20.9. Mass spectrum (70 eV; EI) m/z 250 (0.4%, M+•), 235 (25), 192
(19), 148 (100), 133 (82), 119 (61), 101 (78), 91 (68).
(4S-cis)-5-[2ꢀ-(Formyl)phenyl]-2,2-dimethyl-1,3-dioxolane-
4-methanol Acetate (14)
A magnetically stirred solution of alcohol (13) (2.26 g, 9.6 mmol)
in anhydrous dichloromethane (40 mL) maintained under a nitrogen
atmosphere was treated with acetic anhydride (5.5 mL, 57.31 mmol,
6 mole equiv.), pyridine (4.7 mL, 57.31 mmol) and then DMAP
(100 mg).The resulting mixture was stirred at 18◦C for 16 h then treated
with acetic anhydride (1.83 mL, 19.1 mmol, 2 mole equiv.) and pyridine
(1.56 mL, 19.1 mmol). After 1 h, NaHCO3 (100 mL of a saturated aque-
ous solution) was added and stirring continued for 0.5 h. The separated
organic layer was washed with NH4Cl (3 × 20 mL of a saturated aque-
ous solution) and brine (1 × 20 mL) then dried (MgSO4), filtered, and
concentrated under reduced pressure to give a yellow oil (2.34 g). Sub-
jection of this material to flash chromatography (silica, 3 : 7 v/v ethyl
acetate/hexane elution) and concentration of the appropriate fractions
(Rf 0.5) gave the title acetate (14) (1.47 g, 55%) as a clear, colourless
oil, [α]D −235.8◦ (c 5.7) (Found: [M – CH•3]+, 263.0918. C15H18O5
requires [M – CH•3]+, 263.0919). νmax (KBr)/cm−1 2988, 2938, 2743,
1743, 1698, 1600, 1576, 1373, 1239, 1214, 1167, 1045, 873, 757. δH
10.03 (1 H, s), 7.88 (1 H, d, J 7.8), 7.79 (1 H, d, J 6.5), 7.63 (1 H, dd,
J 7.8 and 7.5), 7.51 (1 H, dd, J 7.5 and 6.5), 6.01 (1 H, d, J 7.0), 4.95
(1 H, dt, J 7.0 and 5.8), 3.51 (2 H, d, J 5.8), 1.85 (3 H, s), 1.65 (3 H, s),
1.52 (3 H, s). δC 193.4, 170.6, 138.0, 135.5, 134.4, 133.2, 128.4, 127.4,
108.9, 75.6, 75.5, 64.4, 27.7, 25.2, 21.0. Mass spectrum (70 eV; EI) m/z
263 (3%, [M – CH•3]+), 220 (2), 203 (13), 178 (10), 160 (100), 147 (28),
118 (98), 105 (17), 91 (21), 77 (15).
(4S-cis)-5-Phenyl-2,2-dimethyl-1,3-dioxolane-4-methanol (16)
A magnetically stirred solution of acetate (15) (42 mg, 0.17 mmol) in
MeOH (10 mL) was treated with solid potassium carbonate (232 mg,
1.68 mmol, 10 mole equiv.). After 0.5 h the reaction mixture was
diluted with water (30 mL) and extracted with ethyl acetate (3 × 10 mL).
The combined organic phases were then dried (MgSO4), filtered, and
concentrated under reduced pressure to give the title alcohol (16)[6]
(33.4 mg, 96%) as an off-white solid, mp 57–58◦C (lit.[6] mp 57–58◦C)
[α]D –84◦ (c 3.7 in MeOH) [lit.[6] [α]D –112◦ (c 1.2 in CHCl3)], (Found:
[M – CH•3]+, 193.0869. C12H16O3 requires [M – CH•3]+, 193.0865).
νmax (KBr)/cm−1 3436, 2989, 2935, 1494, 1455, 1374, 1265, 1213,
1162, 1048, 902, 859, 742, 701. δH 7.37–7.27 (5 H, complex m), 5.30
(1 H, d, J 7.0), 4.45 (1 H, ddd, J 8.2, 7.0 and 4.4), 3.22 (1 H, dd, J
11.6 and 8.2), 3.08 (1 H, dd, J 11.6 and 4.4), 1.72 (1 H, br s), 1.64 (3 H,
s), 1.49 (3 H, s). δC 136.4, 128.6, 128.3, 126.5, 109.2, 79.1, 78.5, 63.2,
28.0, 25.•5. Mass spectrum (70 eV; EI) m/z 208 (<1%, M+•), 193 (26,
[M – CH3]+), 177 (14), 165 (22), 148 (86), 133 (60), 119 (67), 91 (99),
77 (45), 59 (100).
(4R-cis)-2,2-Dimethyl-5-phenyl-1,3-dioxolane-
4-carboxaldehyde (17)
A magnetically stirred mixture of alcohol (16) (35.9 mg, 0.172 mmol),
NMO (61 mg, 0.521 mmol, ca. 3 mole equiv.), and activated pow-
dered molecular sieves (4 Å, ca. 150 mg) in anhydrous dichloromethane
(5 mL), maintained under a nitrogen atmosphere at 0◦C, was treated
with tetrapropylammonium perruthenate(vii) (10.4 mg, 0.03 mmol, ca.
17 mol%). After 1 h the reaction mixture was filtered through a pad
of Celite covering an equivalent pad of TLC-grade silica gel. The
‘column’ comprising these two adsorbents was eluted with additional
dichloromethane (30 mL) and the combined filtrates were concentrated
under reduced pressure to give the title aldehyde (17)[6] (21.9 mg, 62%)
as a clear, light-yellow oil, [α]D –33◦ (c 2.9 in MeOH) (Found: [M –
CH•3]+, 191.0707. C12H14O3 requires [M – CH•3]+, 191.0708). νmax
(KBr)/cm−1 2989, 2917, 1734, 1455, 1381, 1263, 1217, 1158, 1062,
909, 740. δH (CD2Cl2) 9.13 (1 H, d, J 3.1), 7.37–7.31 (5 H, complex
m), 5.48 (1 H, d, J 7.8), 4.59 (1 H, dd, J 7.8 and 3.1), 1.74 (3 H, s),
1.53 (3 H, s). δC (CD2Cl2) 199.7, 134.9, 128.9, 128.7, 126.7, 111.5,
83.1, 79.9, 27.2, 25.2. Mass spectrum (70 eV; EI) m/z 191 (10%, [M –
CH•3]+), 177 (40), 148 (43), 119 (68), 100 (52), 91 (100), 85 (70), 77
(36), 65 (30).
Bis[1,3-bis(diphenylphosphino)propane]rhodium Tetrafluoroborate
and Bis[1,3-bis(diphenylphosphino)propane]dioxorhodium
Tetrafluoroborate
The yellow-red coloured bis[1,3-bis(diphenylphosphino)propane]-
rhodium tetrafluoroborate was prepared according to the method of
James and Mahajan[22] but was observed to turn to a tan-coloured
and crystalline solid on attempted dissolution in various solvents. 31P
NMR and single-crystal X-ray analyses (see Crystallography section,
Fig. 3, Tables 4 and 5) of the latter established it to be bis[1,3-
bis(diphenylphosphino)propane]dioxorhodium tetrafluoroborate. Heat-
ing an acetone solution of this tan-coloured complex under a
nitrogen atmosphere for 16 h followed by concentration of the
cooled solution under reduced pressure, dissolution of the residue
in deoxygenated dichloromethane, and layering this with degassed
diethyl ether resulted in the formation of yellow-red crystals of
[Rh(dppp)2]+BF4−·2CH3COCH3, which could be employed in the
decarbonylation of compound (14) as described below.
(4S-cis)-5-Phenyl-2,2-dimethyl-1,3-dioxolane-
4-methanol Acetate (15)
(αR,4S,5R)-2,2-Dimethyl-5-phenyl-α-propenyl-1,3-dioxolane-
4-methanol (18) and (αS,4S,5R)-2,2-Dimethyl-5-phenyl-α-propenyl-
1,3-dioxolane-4-methanol (19)
A degassed solution of aldehyde (14) (660 mg, 2.37 mmol) in xylene
(8 mL) was added, by cannula, to bis[1,3-bis(diphenylphosphino)
propane]rhodiumtetrafluoroborate[21,22] (120 mg, 0.12mmol, 5 mol%).
The resulting mixture was heated at reflux with stirring for 16 h then
another portion (5 mol%) of catalyst was added and heating was contin-
ued for a further 6 h. The cooled reaction mixture was then diluted with
diethyl ether (20 mL) and filtered through a pad of Celite which was
washed with diethyl ether (20 mL). The combined filtrates were con-
centrated under reduced pressure and the resulting brown oil subjected
to flash chromatography (silica gel, 10–30% v/v ethyl acetate in hexane,
gradient elution), thereby yielding two fractions, A and B.
Allyltributylstannane (200 µL, 0.645 mmol) was added to a magneti-
callystirredsolutionofcompound(17)(44.7 mg, 0.217mmol)inlithium
perchlorate (2 mL of a 5 M solution in diethyl ether). The resultant solu-
tion was stirred under an atmosphere of nitrogen at 18◦C for 4 h then
cooled to 0◦C and quenched by the addition of pH 7 buffer solution
(5 mL). The ensuing mixture was diluted with water (20 mL) and then
extracted with dichloromethane (3 × 5 mL). The combined organic por-
tions were washed with water (1 × 5 mL) and brine (1 × 5 mL) before
being dried (Na2SO4), filtered, and concentrated under reduced pressure

A Total Synthesis of the Styryllactone (+)-Goniodiol from Naphthalene
593
to afford a colourless oil. Subjection of this material to flash chromato-
graphy (silica, 5 : 95 → 2 : 3 v/v ethyl acetate/hexane gradient elution)
provided, after concentration of the appropriate fractions (Rf 0.26 in 3 : 7
v/v ethyl acetate/hexane), a ca. 8 : 3 mixture of compounds (18) and (19)
(37.8 mg, 70%) as a clear, colourless oil. Subjection of this material to
semi-preparative reverse-phase HPLC afforded two fractions, A and B.
Concentration of fraction A (Rt 23.1 min) afforded compound (18)
as a clear, colourless oil, [α]D –31.7◦ (c 1.4) (Found: M+•, 248.1423.
C15H20O3 requires M+•, 248.1412). νmax (NaCl)/cm−1 3501, 2985,
2916, 1640, 1495, 1455, 1380, 1213, 1161, 1054, 915, 876, 700. δH
7.39–7.26 (5 H, complex m), 5.64 (1 H, m), 5.27 (1 H, d, J 6.9), 4.95
(1 H, m), 4.83 (1 H, m), 4.19 (1 H, t, J 6.7), 3.36 (1 H, m), 2.19 (1 H, d,
J 3.4), 1.79 (2 H, m), 1.67 (3 H, s), 1.50 (3 H, s). δC 136.4 (C), 134.4
(CH), 128.5 (CH), 128.3 (CH), 127.1 (CH), 117.3 (CH2), 108.7 (C),
80.7 (CH), 79.1 (CH), 69.5 (CH), 37.8 (CH2), 27.4 (CH3), 25.2 (CH3).
5.80–5.56 (3 H, complex m), 5.31 (1 H, d, J 6.7), 4.96 (1 H, br d, Jca.
9.5), 4.95 (1 H, br d, Jca. 18.2), 4.66 (1 H, ddd, J 8.3, 6.1 and 4.2),
4.47 (1 H, dd, J 8.3 and 6.7), 2.42–2.34 (2 H, complex m), 1.65 (3 H, s),
1.48 (3 H, s). δC 164.3 (C), 136.2 (C), 133.1 (CH), 130.2 (CH2), 128.3
(CH), 128.1 (CH), 128.0 (CH), 126.9 (CH), 118.0 (CH2), 108.8 (C),
79.2 (CH), 78.1 (CH), 71.3 (CH), 35.2 (CH2), 27.3 (CH3), 25.0 (CH3).
Mass spectrum m/z 302 (19%, M+ ), 287 (85, [M – CH•3]+), 244 (56),
•
230 (8), 203 (6), 148 (100), 138 (27), 91 (22), 55 (70).
(6R)-6-[(4S,5R)-2,2-Dimethyl-5-phenyl-1,3-dioxolan-4-yl]-
5,6-dihydro-2H-pyran-2-one (22)
(Cy3P)2Cl2Ru CHPh (4 mL of a 2.5 mM solution in degassed
dichloromethane, 10.0 µmol) was added, in four portions over a 6 h
period, to a magnetically stirred solution of compound (20) (12.6 mg,
41.7 µmol) in degassed dichloromethane (20 mL) maintained under
nitrogen. The resulting solution was stirred at 18◦C for 4 h, treated with
dimethyl sulfoxide (DMSO) (71 µL, 1.0 mmol), left stirring at 18◦C for
16 h, and then concentrated underreduced pressure to afford ayellow oil.
Subjection of this material to flash chromatography (silica, 1 : 4→3 : 2
v/v ethyl acetate/hexane gradient elution) provided, after concentration
of the appropriate fractions (Rf 0.2 in 2 : 3 v/v ethyl acetate/hexane),
compound (22)[11] (9.0 mg, 79%) as colourless needles, mp 137–138◦C,
[α]D –95.1◦ (c 0.45inEtOH)(Found:[M – CH•3]+, 259.0970. C16H18O4
requires [M – CH• ]+, 259.0970). νmax (NaCl)/cm−1 2984, 2932, 1716,
1494, 1455, 13793, 1246, 1216, 1152, 1074, 1062, 1029, 915, 872, 815,
744, 700. δH 7.48–7.44 (2 H, complex m), 7.39–7.27 (3 H, complex m),
6.67 (1 H, ddd, J 9.7, 6.2 and 2.5), 5.86 (1 H, ddd, J 9.7, 2.5 and 0.9),
5.33 (1 H, d, J 6.9), 4.34 (1 H, dd, J 6.9 and 4.0), 4.00 (1 H, dt, J 12.2
and 4.0), 2.40 (1 H, ddt, J 18.2, 12.2 and 2.5), 1.85 (1 H, dddd, J 18.2,
6.2, 4.0 and 0.9), 1.69 (3 H, s), 1.51 (3 H, s). δC 163.1 (C), 144.3 (CH),
135.7 (C), 128.4 (CH), 128.3 (CH), 127.3 (CH), 121.1 (CH), 109.9 (C),
79.4 (CH), 79.1 (CH), 75.6 (CH), 26.6 (CH3), 25.9 (CH2), 25.3 (CH3).
Mass spectrum m/z 259 (33%, [M – CH•3]+), 216 (29), 148 (56), 119
(41), 111 (43), 97 (62), 82 (64), 71 (72), 57 (100).
Mass spectrum m/z 248 (4%, M+ ), 233 (36, [M – CH•3]+), 207 (10),
•
177 (6), 148 (100), 119 (52), 91 (51), 59 (26).
Concentration of fraction B (Rt 25.4 min) afforded compound (19)
as a clear, colourless oil, [α]D –55.9◦ (c 0.5) (Found: M+•, 248.1419.
C15H20O3 requires M+•, 248.1412). νmax (NaCl)/cm−1 3585, 3470,
3073, 2988, 2916, 2849, 1640, 1495, 1455, 1381, 1259, 1214, 1161,
1054, 875, 752, 700. δH 7.44–7.26 (5 H, complex m), 5.75 (1 H, m),
5.33 (1 H, d, J 6.6), 5.08 (1 H, m), 5.04 (1 H, m), 4.17 (1 H, dd, J 8.8
and 6.6), 3.40 (1 H, m), 2.46 (1 H, m), 2.15 (1 H, m), 1.62 (3 H, s), 1.48
(3 H, s), 0.96 (1 H, d, J 4.1). δC 137.1 (C), 134.5 (CH), 128.6 (CH),
128.3 (CH), 127.3 (CH), 118.0 (CH2), 108.7 (C), 81.0 (CH), 79.4 (CH),
69.2 (CH), 38.2 (CH2), 27.4 (CH3), 25.0 (CH3). Mass spectrum m/z
248 (21%, M+ ), 233 (60, [M – CH•3]+), 207 (5), 177 (5), 148 (100),
•
119 (41), 91 (38).
(αR,4S,5R)-2,2-Dimethyl-5-phenyl-α-propenyl-1,3-dioxolane-
4-methanol Acrylate (20)
A magnetically stirred solution of alcohol (18) (27.4 mg, 0.11 mmol)
and DMAP (108 mg, 0.88 mmol, ca. 8 mole equiv.) in anhydrous THF
(1 mL) maintained at −20◦C under a nitrogen atmosphere was treated,
dropwise, with acrylic anhydride (1.7 mL of a 0.26 M solution in THF,
0.44 mmol, ca. 20 mole equiv.). After completion of the addition the
solution was warmed to 18◦C, stirred for 3 h, and the reaction mixture
was then diluted with NH4Cl (20 mL of a saturated aqueous solu-
tion). The separated aqueous phase was extracted with ethyl acetate
(3 × 10 mL) and the combined organic phases dried (MgSO4), filtered,
andconcentratedunderreducedpressuretogiveabright-yellowoil. Sub-
jection of this material to flash chromatography (silica gel, 1 : 9 v/v ethyl
acetate/hexane elution) afforded, after concentration of the appropriate
fractions (Rf 0.2), compound (20) (15.6 mg, 47%) as a white crys-
talline solid, mp 42–43◦C, [α]D −94.5◦ (c 1.1) (Found: M+•, 302.1529.
C18H22O4 requires M+•, 302.1518). νmax (NaCl)/cm−1 3078, 2985,
2936, 1727, 1638, 1405, 1296, 1269, 1249, 1216, 1191, 1059, 985, 879,
805, 736, 701. δH 7.36–7.24 (5 H, complex m), 6.32 (1 H, dd, J 17.4
and 1.4), 6.04 (1 H, dd, J 17.4 and 10.4), 5.80 (1 H, dd, J 10.4 and 1.4),
5.62 (1 H, m), 5.34 (1 H, d, J 7.2), 5.01 (1 H, m), 4.96 (1 H, m), 4.65
(1 H, dt, J 6.3 and 4.6), 4.44 (1 H, dd, J 7.2 and 4.6), 2.09 (2 H, m),
1.67 (3 H, s), 1.50 (3 H, s). δC 165.1 (C), 136.3 (C), 133.2 (CH), 130.5
(CH2), 128.9 (CH), 128.5 (CH), 128.2 (CH), 126.7 (CH), 118.3 (CH2),
109.1 (C), 78.6 (CH), 78.5 (CH), 71.4 (CH), •35.8 (CH2), 26.9 (CH3),
25.4 (CH3). Mass spectrum m/z 302 (3%, M+ ), 287 (43, [M – CH3• ]+),
244 (20), 148 (100), 138 (22), 119 (21), 91 (21), 55 (74).
(6S)-6-[(4S,5R)-2,2-Dimethyl-5-phenyl-1,3-dioxolan-4-yl]-
5,6-dihydro-2H-pyran-2-one (23)
Subjection of diene (21) (12.0 mg, 0.040 mmol) to ring-closing metathe-
sis in the same manner as described immediately above and used
for congener (20) afforded a light-yellow oil on workup. This mate-
rial was subjected to flash chromatography (silica, 1 : 4 → 1 : 1 v/v
ethyl acetate/hexane gradient elution) providing, after concentration
of the appropriate fractions (Rf 0.2 in 3 : 7 v/v ethyl acetate/hexane),
compound (23) (7.9 mg, 73%) as colourless needles, mp 97–98◦C,
•
[α]D –27.3◦ (c 0.4) (Found: M+•, 274.1212. C16H18O4 requires M+
,
274.1205). νmax (NaCl)/cm−1 2988, 2920, 1734, 1494, 1455, 1382,
1246, 1213, 1162, 1065, 1034, 984, 864, 815, 745, 700. δH 7.40–7.27
(5 H, complex m), 6.74 (1 H, ddd, J 9.8, 6.3 and 2.4), 5.83 (1 H, dd,
J 9.8 and 2.4), 5.43 (1 H, d, J 7.1), 4.54 (1 H, t, Jca. 7.1), 3.98 (1 H,
ddd, J 11.2, 7.1 and 3.9), 2.43 (1 H, ddt, J 18.6, 11.2 and 2.4), 2.23
(1 H, ddd, J 18.6, 6.3 and 3.9), 1.65 (3 H, s), 1.49 (3 H, s). δC 162.9
(C), 145.1 (CH), 136.7 (C), 128.4 (CH), 128.3 (CH), 127.1 (CH), 121.1
(CH), 109.3 (C), 79.1 (CH), 78.8 (CH), 75.9 (CH), 26.8 (CH3), 26.0
(CH2), 24.6 (CH3). Mass spectrum m/z 274 (2%, M+•), 259 (32, [M –
CH•3]+), 216 (47), 177 (10), 148 (95), 133 (13), 119 (38), 100 (50), 97
(68), 82 (100).
(αS,4S,5R)-2,2-Dimethyl-5-phenyl-α-propenyl-1,3-dioxolane-
4-methanol Acrylate (21)
(+)-Goniodiol {(6R)-6-[(1R,2R)-1,2-Dihydroxy-2-phenylethyl]-
5,6-dihydro-2H-pyran-2-one} (1)
Acrylation of alcohol (19) (19.1 mg, 0.77 mmol) in the same manner as
used for congener (18) (see immediately above) afforded a light-yellow
oil on workup. Subjection of this material to flash chromatography (sil-
ica gel, 1 : 9 v/v ethyl acetate/hexane elution) gave, after concentration
of the appropriate fractions (Rf 0.2), compound (21) (12.2 mg, 52%)
as a white crystalline solid, mp 36–38◦C, [α]D –11.1◦ (c 0.6) (Found:
M+•, 302.1518. C18H22O4 requires M+•, 302.1518). νmax (NaCl)/cm−1
2986, 1727, 1639, 1405, 1381, 1263, 1188, 1057, 984, 917, 879, 806,
699. δH 7.32–7.17 (5 H, complex m), 6.10 (1 H, dd, J 17.1 and 1.5),
A magnetically stirred solution of acetonide (22) (4.4 mg, 16.0 µmol)
in acetic acid/water (4 mL of a 1 : 1 v/v mixture) was heated at 80◦C for
0.5 h then cooled to 0◦C and pH 7 buffer solution (20 mL) was added.
The resulting mixture was diluted with brine (10 mL) then extracted
with ethyl acetate (4 × 10 mL). The combined organic portions were
dried (Na2SO4), filtered, and concentrated under reduced pressure to
give a colourless oil. Subjection of this material to flash chromato-
graphy (silica, 1 : 4 → 4 : 1 v/v ethyl acetate/dichloromethane gradi-
ent elution) provided, after concentration of the appropriate fractions

594
M. G. Banwell et al.
(Rf 0.25 in 3 : 2 v/v ethyl acetate/dichloromethane), (+)-goniodiol
(1)[1,2] (3.7 mg, 98%) as a clear, colourless oil, [α]D +72.1◦ (c
0.3 in CHCl3) [lit.[2] [α]D +74.4◦ (c 0.3 in CDCl3)] (Found:
[M + Na]+, 257.0782. C13H14O4 requires [M + Na]+, 257.0784). νmax
(NaCl)/cm−1 3409, 2923, 1704, 1389, 1259, 1029, 817, 701. δH
(500 MHz) 7.44–7.32 (5 H, complex m), 6.93 (1 H, ddd, J 9.0, 6.5 and
2.0), 6.00 (1 H, dd, J 9.0 and 2.5), 4.95 (1 H, dd, J 7.5 and 5.5), 4.80
(1 H, m), 3.73 (1 H, m), 2.80 (1 H, m), 2.65 (1 H, d, J 5.5), 2.32 (1 H,
d, J 8.5), 2.18 (1 H, ddd, J 18.5, 6.0 and 3.5). δC (125 MHz) 163.6,
146.1, 140.7, 128.8, 128.4, 126.5, 120.6, 75.0, 73.7, 26.1 (one signal
obscured by resonances due to CDCl3). Mass spectrum (ESI) m/z 491
(18%, [2M + Na]+), 257 (100, [M + Na]+).
(2). Generous financial support from the Institute of
Advanced Studies and the Australian Research Council is
warmly acknowledged. Professors S. V. Ley (University of
Cambridge) and W.-S. Zhou (Shanghai Institute of Organic
Chemistry) are thanked for providing spectral data derived
from synthetic samples of compounds (1) and (22).Technical
assistance from Dr Eric Wenger (Research School of Chem-
istry) and Dr Carl Braybrook (CSIRO Molecular Science,
Melbourne) is gratefully acknowledged.
References
6-epi-(+)-Goniodiol {(6S)-6-[(1R,2R)-1,2-Dihydroxy-
2-phenylethyl]-5,6-dihydro-2H-pyran-2-one} (24)
[1] S. K. Talapatra, D. Basu, T. Deb, S. Goswami, B. Talapatra,
Indian J. Chem., Sect. B 1985, 24, 29.
[2] X.-P. Fang, J. E. Anderson, C.-J. Chang, J. L. McLaughlin,
J. Nat. Prod. 1991, 54, 1034.
[3] G. C. L. Ee, H. L. Lee, S. H. Goh, Nat. Prod. Lett. 1999,
13, 137.
[4] J.-P. Surivet, J.-M. Vatele, Tetrahedron 1999, 55, 13 011.
[5] (a) M. Tsubuki, K. Kanai, T. Honda, J. Chem. Soc., Chem.
Commun. 1992, 1640. (b) M. Tsubuki, K. Kanai, H. Nagase,
T. Honda, Tetrahedron 1999, 55, 2493.
[6] (a) Z.-C. Yang, W.-S. Zhou, J. Chem. Soc., Chem. Commun.
1995, 743. (b) Z.-C. Yang, W.-S. Zhou, Heterocycles 1997,
45, 367.
[7] (a) J.-P. Surivet, J. Goré, J.-M. Vatele, Tetrahedron Lett. 1996,
37, 371. (b) J.-P. Surivet, J. Goré, J.-M. Vatele, Tetrahedron
1996, 52, 14 877.
[8] J.-P. Surivet, J.-N. Volle, J.-M. Vatele, Tetrahedron: Asymmetry
1996, 7, 3305.
Hydrolysis of acetonide (23) (7.4 mg, 27.0 µmol) in the same man-
ner as described immediately above for congener (22) afforded a clear,
colourless oil on workup. Subjection of this material to flash chromato-
graphy (silica, 1 : 4 → 4 : 1 v/v ethyl acetate/dichloromethane gradient
elution) provided, after concentration of the appropriate fractions (Rf
0.3 in 1 : 1 v/v ethyl acetate/dichloromethane), 6-epi-(+)-goniodiol (24)
(5.4 mg, 85%) as a clear, colourless oil, [α]D –47.4◦ (c 0.27) (Found:
M+•, 234.0895. C13H14O4 requires M+•, 234.0892). νmax (NaCl)/cm−1
3405, 2913, 1701, 1389, 1261, 1075, 1038. δH 7.44–7.32 (5 H, complex
m), 6.92 (1 H, ddd, J 9.8, 6.3 and 2.2), 5.98 (1 H, dd, J 9.8 and 2.2),
4.92 (1 H, d, J 5.4), 4.37 (1 H, dt, Jca. 12.6 and 5.4), 4.17 (1 H, br t, J
5.4), 2.68 (1 H, ddt, J 18.4, 12.6 and 2.2), 2.54–2.47 (3 H, complex m).
δC 164.0 (C), 146.1 (CH), 139.7 (C), 128.8 (CH), 128.6 (CH), 126.9
(CH), 120.9 (CH), 78.1 (CH), 74.9 (CH), 73.9 (CH), 24.6 (CH2). Mass
•
spectrum m/z 234 (35%, M+ ), 216 (3, [M – H2O]+•), 188 (3), 177 (5),
144 (5), 128 (37), 107 (100), 69 (56).
[9] J.-P. Surivet, J.-M. Vatele, Tetrahedron Lett. 1998, 39, 7299.
[10] C. Muka, S. Hirai, M. Hanaoka, J. Org. Chem. 1997, 62, 6619.
[11] D. J. Dixon, S. V. Ley, E. W. Tate, J. Chem. Soc., Perkin Trans.
1 1998, 3125.
Crystallography
Crystal Data
[12] J. Chen, G.-Q. Lin, Z.-M. Wang, H.-Q. Liu, Synlett 2002, 1265.
[13] P. V. Ramachandran, J. S. Chandra, M. V. R. Reddy, J. Org.
Chem. 2002, 67, 7547.
[14] For an excellent review on the production and general synthetic
utility of these types of compounds see T. Hudlicky, D. Gonzalez,
D. T. Gibson, Aldrichimica Acta 1999, 32, 35.
[15] M. G. Banwell, A. J. Edwards, G. J. Harfoot, K. A. Jolliffe,
M. D. McLeod, K. J. McRae, S. G. Stewart, M. Vögtle, Pure
Appl. Chem. 2003, 75, 219.
[16] M. G. Banwell, V. S. Bridges, J. R. Dupuche, S. L. Richards,
J. M. Walter, J. Org. Chem. 1994, 59, 6338.
[17] V. VanRheenen, R. C. Kelly, D. Y. Cha, Tetrahedron Lett. 1976,
1973.
Compound (8). C16H20O4, M 276.33, T 200 K, monoclinic, space
group P21,
a 9.4227(3), b 6.4126(2), c 12.1884(5) Å, β
100.8003(14)◦, V 723.43(4) Å3, Z 2, Dc 1.269 g cm−3, µ 0.90 cm−1
,
λ(MoKα) 0.71073 Å, 1799 unique data (2θmax 54.86◦), 1223 with
I > 2σ(I), R 0.031, wR 0.029, S 1.069. See Tables 1 and 2 for selected
bond lengths and angles.
[Rh(dppp)2O2]+BF− · 2CH3COCH3. C60H64BF4O4P4Rh, M
1162.772, T 200 K, mon4oclinic, space group P 21/n, a 11.70970(10),
b 14.65970(10), c 32.0154(3) Å, β 98.8272(3)◦, V 5430.69(8) Å3, Z 4,
Dc 1.422 g cm−3, µ 4.9 cm−1, λ(MoKα) 0.71073 Å, 12805 unique data
(2θmax 55.8◦), 4765 with I > 3σ(I), R 0.045, wR 0.051, S 1.041. See
Tables 3 and 4 for selected bond lengths and angles.
[18] K. J. Henry, P. A. Grieco, C. T. Jagoe, Tetrahedron Lett. 1992,
33, 1817.
[19] G. M. Whited, J. C. Downie, T. Hudlicky, S. P. Fearnley,
T. C. Dudding, H. F. Olivo, D. Parker, Bioorg. Med. Chem.
1994, 2, 727.
[20] M. A. Andrews, G. L. Gould, S. A. Klaeren, J. Org. Chem.
1989, 54, 5257.
[21] M. A. Aubart, L. H. Pignolet, ‘Bis[1,3-bis(diphenylphosphino)
propane]rhodium tetrafluoroborate’, in Encyclopedia of
Reagents for Organic Synthesis (Ed. L. A. Paquette) 1995
(John Wiley and Sons: Chichester).
[22] B. R. James, D. Mahajan, Can. J. Chem. 1980, 58, 996.
[23] J. A. McGinnety, N. C. Payne, J. A. Ibers, J. Am. Chem. Soc.
1969, 91, 6301.
[24] M. S. VanNieuwenhze, K. B. Sharpless, Tetrahedron Lett. 1994,
35, 843.
Structure Determination
Intensity data were collected on a Nonius Kappa CCD diffractometer
and extracted from diffraction images using the DENZO[40] package.
Analytical absorption corrections were applied.[41] Both structures were
solved by direct methods[42] and expanded using Fourier techniques.[43]
Full-matrix least-squares refinement[43] was on F, non-hydrogen atoms
were refined anisotropically while hydrogen atoms were included at geo-
metrically determined positions and ride on the carbon of attachment.
For structure (8) hydrogen atoms attached to oxygen were refined. Sig-
nificant but readily modelled disorder was observed for both the BF4−
anionandsolvatingacetonemolecules(seeCIFfordetaileddescription).
Atomic coordinates, bond lengths and angles, and displacement
parameters have been deposited with the Cambridge Crystallographic
Data Centre (CCDC Nos 198403 and 198404 for compound (8) and the
ruthenium complex, respectively).
[25] D. Xu, K. B. Sharpless, Tetrahedron Lett. 1994, 35, 4685.
[26] W. P. Griffth, S. V. Ley, Aldrichimica Acta 1990, 23, 13.
[27] S. Florio, V. Capriati, ‘Allylmagnesium Bromide’, in Encyclo-
pedia of Reagents for Organic Synthesis (Ed. L. A. Paquette)
1995 (John Wiley and Sons: Chichester).
Acknowledgments
Dr Gregg Whited (Genencor International, Palo Alto) is
thanked for providing substantial quantities of the diol

A Total Synthesis of the Styryllactone (+)-Goniodiol from Naphthalene
595
[28] M. T. Reetz, K. Kesseler, A. Jung, Tetrahedron Lett. 1984,
25, 729.
[29] C. H. Heathcock, S. Kiyooka, T. A. Blumenkopf, J. Org. Chem.
1984, 49, 4214.
[36] For useful reviews dealing with chelation-controlled processes
see (a) A. Mengel, O. Reiser, Chem. Rev. 1999, 99, 1191. (b)
M. T. Reetz, Acc. Chem. Res. 1993, 26, 462.
[37] D. Longbottom, Synlett 1999, 2023.
[30] H. C. Brown, K. S. Bhat, R. S. Randad, J. Org. Chem. 1989,
54, 1570.
[31] B. W. Gung, X. Xue, W. R. Roush, J. Am. Chem. Soc. 2002,
124, 10 692, and references therein.
[38] T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
[39] (a) Y. Du, D. F. Wiemer, Tetrahedron Lett. 2001, 42, 6069, and
references therein. (b) B. M. Trost, V. S. C. Yeh, Org. Lett.
2002, 4, 3513.
[32] Y. Yamamoto, K. Maruyama, K. Matsumoto, J. Chem. Soc.,
Chem. Commun. 1983, 489.
[33] M. Shimagaki, H. Takubo, T. Oishi, Tetrahedron Lett. 1985, 26,
6235.
[40] Z. Otwinoski, W. Minor, Methods Enzymol. 1997, 276, 307.
[41] P. Coppens, in Crystallographic Computing (Eds F. R. Ahmed,
S. R. Hall, C. P. Huber) 1970, pp. 255–270 (Munksgaard:
Copenhagen).
[34] G. E. Keck, K. A. Savin, E. N. K. Cressman, D. E. Abbott,
J. Org. Chem. 1994, 59, 7889.
[35] For a useful discussion of the allylation of related systems
see M. Carda, E. Castillo, S. Rodriguez, F. Gonzalez, J. A.
Marco, Tetrahedron: Asymmetry 2001, 12, 1417, and references
therein.
[42] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano,
C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori,
R. Spagna, J. Appl. Crystallogr. 1999, 32, 115.
[43] D. J. Watkin, C. Prout, J. R. Carruthers, P. W. Betteridge,
R. I. Cooper, CRYSTALS Issue 11 2001 (Chemical Crystallo-
graphy Laboratory: Oxford).