An unexpected (3 → 2)-hydride shift in phyllocladane (=13β-kaurane) diterpenoids and in related trimethyl-substituted Bi- and tricyclic compounds

Article abstract of DOI:10.1002/hlca.200390044

The conversion of 2α,3α-dioxy-substituted phyllocladane derivatives into the corresponding 3-ketone proceeds in an unexpected manner: Depending on the reaction conditions, the corresponding 3β-hydroxy-substituted compound is formed almost quantitatively,

Full text of DOI:10.1002/hlca.200390044

Helvetica Chimica Acta Vol. 86 (2003)
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An Unexpected (3 ! 2)-Hydride Shift in Phyllocladane (ˆ13b-Kaurane)
Diterpenoids and in Related Trimethyl-Substituted Bi- and Tricyclic
Compounds
by Ralph M¸ller and Peter R¸edi*
Organisch-chemisches Institut der Universit‰t Z¸rich,Winterthurerstrasse 190, CH-8057 Z¸rich
The conversion of 2a,3a-dioxy-substituted phyllocladane derivatives into the corresponding 3-ketone
proceeds in an unexpected manner: Depending on the reaction conditions, the corresponding 3b-hydroxy-
substituted compound is formed almost quantitatively, or the desired ketone can be isolated directly (see
preceding paper). The reaction mechanism is now disclosed to be a stereospecific C(3) ! C(2)-hydride shift by
investigating the reactions of the synthesized (Æ)-trans-decalin-type (trans-1,5,5-trimethylbicyclo[4.4.0]decanes)
and (Æ)-podocarpane-type (trans-1,2,3,4,4a,9,10,10a-octahydro-1,1,4a-trimethylphenanthrenes) model com-
pounds 25 and 35 and of their D-labeled isomers 25' and 35' (Scheme 6). The latter afforded the corresponding
3b-hydroxy (2b-D)-derivatives 38 and 39 as well as the (2b-D)-3-ketones of the general type 5b' (e.g., 36'), thus
evidencing a suprafacial (C3) ! C(2)-deuteride shift. This reaction mechanism seems to be a general feature of
such 3a,4a-dioxy-substituted 1,5,5-trimethylbicyclo[4.4.0]decane congeners.
1. Introduction. In the preceding paper [1], we reported that the attempted
chemical transformation of the natural phyllocladane 1 into the 3-oxo derivative 5a
(calliterpenone; Scheme 1) yielded exclusively the 3b-hydroxy derivative 6 when the
2a,3a-diol 2-tosylate 3 was treated with LiAlH4 (Scheme 2). Although the favorable
conformations of 3 meet neither the steric nor the stereoelectronic requirements, this
unexpected reaction was a priori considered to proceed via an elimination, yielding an
enol(ate) and stereospecific reduction of the corresponding ketone 5b [1]. This
hypothesis was strongly supported by the observation that 3 reacts with LiAlD4 to
generate exclusively the 3a-deutero compound 6'1). However, closer investigation of
Scheme 1
1
)
The D-labeled isomers are characterized by a prime (') added to the number of the corresponding
unlabeled isomer.

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Scheme 2
a) TsCl, pyridine, r.t.; 94%. b) TsCl, pyridine, D; 50% (‡47% of starting 2). c) LiAlH4 or LiAlD4, THF, r.t.; 6
(90%), 6' (92%) [1]. d) Pyridine or toluene, D; 89 and 98%, resp. e) NaOEt or NaH, r.t.; 52 and 49%, resp. f)
PCC, NaOAc, CH2Cl2, r.t.; 95%.
this reaction (see Exper. Part) precluded the formation of an intermediate enol since
reaction of 3 with LiAlH4 or LiAlD4 in (D4)THF and workup with D2O yielded only 6,
and no trace of the expected DÀC(2) was observed. But, surprisingly, ketone 5b could
be obtained directly when the 2a,3a-diol 2 was refluxed in pyridine in the presence of p-
toluenesulfonyl chloride (TsCl) or by heating the neat tosylate 3 in pyridine or toluene
(Scheme 2). As a consequence, LiAlH4 was assumed to promote the key step of the
reaction as a base, rather than being a reducing agent. This could be demonstrated by
the successful transformation of the tosylate 3 by NaOEt or NaH, which yielded also 5b
(Scheme 2). In addition, refluxing the bis-methanesulfonate derivative 4 in pyridine or
toluene left the starting material unchanged, and treatment of 4 with NaOEt or NaH
afforded diol 2 by hydrolysis, whereas reaction of 4 with LiAlH4 was known [1] to yield
mainly the corresponding 2b-hydroxy compound. These experimental results lead to
the formulation of a reaction mechanism for the key step in terms of a suprafacial
C(3) ! C(2)-hydride shift/elimination process as depicted in Scheme 3.
To verify these assumptions, the reaction pathway was tracked by the (3b-D)-
isomers of the general type 2' and 3' (Scheme 3). In the following, we report the
syntheses and reactions of 2' and 3' and of their (Æ)-trans-decalin-type (trans-1,5,5-
Scheme 3

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441
trimethylbicyclo[4.4.0]decanes) and (Æ)-podocarpane-type (trans-1,2,3,4,4a,9,10,10a-
octahydro-1,1,4a-trimethylphenanthrenes) congeners 25, 25', 35, and 35'2).
2. Results and Discusssion.
2.1. Attempted Partial Syntheses of the (3b-
D)Phyllocladanes 2' and 3' (Scheme 4). Reaction of 3 and 5b with LiAlH4 or LiAlD4
yielded the 3b-hydroxy compounds 6 and 6' [1], which were mesylated ( ! 7 and 7') and
afforded the olefins 8 and 8' after forced elimination [2] from the unfavorable
conformation. Every attempt to hydroxylate the phylloclad-2-ene 8 by the current
methods (e.g., OsO4 and modifications [3], KMnO4, etc.) failed, although there are
several reports of successful similar transformations [4]3).
Aiming at the stereospecific reduction of the C(3)-carbonyl group, the 16,17-
acetonide 9 of the natural product [1] was then studied. According to reports on similar
compounds [4d][6], a significant proportion of the 3a-hydroxy compound should be
formed4), although the 3b-alcohol is a priori expected to be the predominant reduction
product. However, all attempts to prepare the 3a-alcohol 10 failed as the attack of the
reducing agents exclusively took place from the sterically less-hindered −a-side×, and
only the undesired 3b-hydroxy isomers 11, 11', 12, and 12' could be obtained, the latter
two being the products of acyl migration (see also [6d]). A drawback that precluded
many promising combinations of complexing and (chiral) reducing reagents is the
lability of both the 2a-oxy-3-oxo and the 16,17-acetonide moieties, and the limited
amount of natural material particularly prevented an extensive search for the optimal
reaction conditions. Moreover, all efforts to achieve the obvious inversion of the
configuration at C(3) in 11 and 11' by standard SN2 procedures or their modifications
(e.g., Mitsunobu reaction) also failed. Due to the diequatorial subsitution, ring A
adopts the strongly favored chair conformation that renders C(3) inaccessible for a
nucleophilic attack.
Although the olefin 8 could not be hydroxylated, it underwent epoxidation either
with 3-chloroperbenzoic acid (MCPBA) or dimethyldioxirane [7] to afford exclusively
the 2a,3a-epoxides 14 and 14', a specificity that was verified by the targeted
preparation of the 2b,3b-diastereoisomer 15 (Scheme 4). However, all attempts to
open 14 and 14' and the following reactions (see later) again did not afford the desired
2a,3a-dihydroxy compounds.
2
)
As all model compounds were prepared as racemates, their structural formulae represent the relative
configurations.
3
)
Because the amounts of the natural phyllocladanes were limited, the hydroxylation reactions were also
studied with triterpenoid model compounds, as exemplified in [4a c]. Derived from the commercially
available dipterocarpol and betulin, ring-A,B,C analogues of phylloclad-2-ene were prepared. However, in
our hands, all experiments to obtain a 2a,3a-diol failed as the 4,4,10-trimethyl-substituted olefins were
completely inert in most cases. This failure might be explained by the fact that we used small amounts
(<50 mg), whereas the successful authors were dealing with gram quantities of both starting materials and
reagents. Moreover, the yields if reported are low and vary from only 3.8% [4d] to a maximum of 36%
[4f]. In contrast, we easily obtained 5a-cholestane-2a,3a-diol in quantitative yield when transforming 5a-
cholest-2-ene (see [5]).
Reduction of a 2a-oxy-3-oxo triterpenoids by NaBH4 [6] or 2a-oxy-3-oxo-ent-beyerenes by LiAlH4 [4d]
afforded the corresponding 3a-alcohols as minor compounds (10% [6a], 13% [6d], 28% [4d]). Surprisingly,
they are also reported to be the main products (68% [6c], 84% [6b]). However, applying the reaction
conditions of [6b] gave no trace of the desired 3a-alcohol 10.
4
)

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Scheme 4
a) LiAlH4 or LiAlD4, THF, r.t.; 6 (95%), 6' (99%) [1]. b) MeSO2Cl, pyridine, r.t.; 7 (94%), 7' (84%). c) LiBr,
Li2CO3, DMF, 1808; 8 (86%), 8' (92%). d) NaBH4 or NaBD4, THF, r.t.; 11 (51%), 11' (52%), 12 (24%), 12'
(24%). e) TsCl, pyridine, r.t.; 16%. f) 0.1m dimethyldioxirane, Ch2Cl2, À308; 36%. g) LiAlH4, THF, r.t.; 68%.
2.2. Syntheses of Model Analogues: (Æ)-trans-Decalins 25 and 25' and (Æ)-
Podocarpanes2) 35 and 35'. We were not able to prepare the required (3b-D)-
phyllocladan-3a-ol derivatives 2' and 3'. The key problem seems to be the 4,4,10-
trimethyl substitution pattern in ring A and the rigidity of the tetracyclic diterpenoid
skeleton [1]. Therefore, the closely related model compounds 25, 25', 35, and 35' were
prepared (Scheme 5) to draw the mechanistic conclusions from their reaction behavior
with respect to the natural products. Prior to the D-labeled isomers 17' 35', the
respective unlabeled isomers 17 35 were characterized, and the synthesis of the

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443
deuterated compounds was then performed analogously5). Reduction of the ketones
16 [8] and 26 [9] with LiAlH4 or LiAlD4 followed by hydrogenation gave the 3b-
alcohols 17 [8a,b][10] and 27 [9b][11] and the (3a-D)-isomers 17' and 27'6). The 3b-
mesylates 18, 18', 28, and 28' were then transformed under forced conditions [2] to the
olefins 19 [12], 19', 29 [11], and 29'. Treatment with dimethyldioxirane [7] afforded the
b-epoxides 20, 20', 30, and 30'. Epoxide opening with PPh3/I2 according to [13] followed
by acetylation furnished the 2b-iodo 3a-acetates 21, 21', 31, and 31'7). The I-substituent
was exchanged under SN2-conditions after reaction with peracetic acid [14]8) to afford
the 2a,3a-diol 3a-acetates 22, 22', 32, and 32'9). The 2a,3a-diols 24, 24', 34 and 34' and
the final target compounds, the 2a,3a-diol 2a-tosylates 25, 25', 35, and 35' were
prepared by standard procedures (Scheme 5).
3.3. Reactions of the (Æ)-trans-Decalins 25 and 25' and of the (Æ)-Podocarpanes 35
and 35'. The unexpected reactions that were detected in the tetracyclic diterpenoid
series could be reproduced with the model compounds (Scheme 6). Hence, upon
reaction with LiAlH4 the 2a,3a-diol 2a-tosylates 25 and 35 afforded the 3b-alcohols 17
and 27, and thermal reaction (pyridine or toluene) or base treatment (NaOEt or NaH)
gave the ketones 36 [8a][10] and 37 [9].
Finally, treatment of the (3b-D)-2a,3a-diol 2a-tosylates 25' and 35' with LiAlH4
afforded the 3b-hydroxy (2b-D)-isomers 38 and 39. The location of the D-atom was
unambiguously inferred from the comparison of the 1H- and 13C-NMR data of the ring-
A H- and C-atoms with those of the unlabeled isomers (see Exper. Part). However, the
attempts to obtain the (2b-D)-3-ketones 36' and 37' by thermal reactions of 25' and 35'
as described above were not successful. Only when the decalin 25' was treated with
NaOEt or NaH at room temperature, the expected 36' could be evidenced (see Exper.
Part); in all other experiments, just the unlabeled ketones 36 or 37 were isolated. This
partial failure can be explained by the stereoelectronically favored enolization of the
axial DÀC(2), as demonstrated by the slow D-exchange when the neat compounds 36'
and 37'10) were kept in solution at room temperature.
3. Conclusions and Remarks. In spite of the restrictions mentioned above, the
experimental results clearly disclose the mechanistic course of the investigated
reaction. The key step is a stereospecific C(3) ! C(2)-hydride shift followed by an
elimination process, fully in accord with the postulated pathway depicted in Scheme 3.
Moreover, as this course was shown to proceed with three different skeletal types
5
)
)
)
)
)
As the steps for the preparation of the podocarpanes are identical to those of the decalins, the description
of the individual synthetic pathways are combined (see also Scheme 5).
The structurally relevant spectroscopic data are similar for the podocarpanes and the phyllocladanes (see
Exper. Part).
6
7
8
9
Ring A adopts the boat conformation, the big I-substituent being in the favorable equatorial position in 21
1
and 21' and 31 and 31' (see H-NMR signals of HÀC(2) in the Exper. Part).
Usually, this transformation is now performed with MCPBA [5][15]. We had useful yields only when
applying the original conditions [14].
Acyl migration ( ! 23, 23', 33, and 33') was observed when transforming 21, 21', 31, and 31', see Exper.
Part.
10
)
The key reference compounds 36' and 37' were accessible after Jones oxidation of 38 and 39, respectively
(Scheme 6 and Exper. Part).

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Scheme 5
as) LiAlH4 or LiAlD4, THF, 08. b) H2, Pd/C, EtOH; 17 (75%), 17' (92%), 27 (88%), 27' (88%). c) MeSO2Cl,
pyridine, r.t.; 18 (66%), 18' (67%), 28 (54%), 28' (54%). d) LiBr, Li2CO3, DMF, 1408; 19 (67%), 19' (95%), 29
(79%), 29' (89%). e) Dimethyldioxirane (0.1m), CH2Cl2, À308 ! r.t.; 20 (76%), 20' (61%), 30 (66%), 30'
(60%). f) PPh3, I2, Ch2Cl2, r.t. g) Ac2O, pyridine, r.t.; 21 (69%), 21' (75%), 32 (85%), 31' (82%). h)
MeCOOOH (40%), CH2Cl2, r.t.; 22 (45%), 22' (49%), 23 (13%), 23' (11%), 32 (43%), 32' (47%). i) LiAlH4,
THF, 08; 24 (85%), 24' (91%), 34 (76%), 34' (74%). j) TsCl, pyridine, r.t.; 25 (93%), 25' (96%), 35 (73%), 35'
(73%).
(phyllocladanes, decalins, and podocarpanes), the reaction mechanism seems to be a
general feature of such 3a,4a-dioxy-substituted 1,5,5-trimethylbicyclo[4.4.0]decane
congeners. It is noteworthy that the prerequisite for such a hydride shift is a good

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445
Scheme 6
a) LiAlH4, THF, r.t.; 17 (86%), 27 (85%), 38 (83%), 39 (89%). b) Pyridine, D: 36 (87%), 37 (86%); or toluene,
D: 36 (90%), 37 (91%). c) NaOEt, r.t.: 36 (51%), 36/36' (47%, ca. 6 :1)), 37 (57%); or NaH, r.t.: 36 (47%), 36/
36' (47%, ca. 6 :1), 37 (57%). d) Jones reagent, r.t.; 36 (83%), 36' (87%), 37 (87%), 37' (86%). 17, 25, 25', 36,
36', 38 ˆ (Æ)-decalins 27, 35, 35', 37, 37', 39 ˆ (Æ)-podocarpanes
electrophilic leaving group at C(3), either in the starting material or at least in an
intermediate as depicted in Scheme 2 (pathway b)).
Related reactions of 2- or 3-(tosyloxy)lanosterol derivatives and selected D-labeled
isomers thereof have been investigated by the group of Levisalles [16]. Besides the
expected olefins, the reaction mixtures that were obtained after treatment with AcOH/
NaOAc contained also significant amounts of products with a surprising distribution of
D-atoms. These findings were rationalized by rather complex and to some extent
speculative mechanisms [16]. In particular, the formation of each unexpected
compound was explained by an individual and specific pathway that holds only for
the respective reaction and its products. Based on our results, all of these reactions can
now be simplified and generalized in terms of hydride shifts similar to those shown in
the key steps of Scheme 3.
The authors are indebted to the Swiss National Science Foundation for financial support and to the
analytical department of our institute for the MS and the AMX-600 and DRX-600 NMR spectra.
Experimental Part
1. General. See [1].
2. (16R)-16,17-(Isopropylidenedioxy)phyllocladan-3-one ( ˆ Calliterpenone 16,17-Acetonide; 5b). A soln.
of 6 (610 mg) in abs. CH2Cl2 (15ml) was added in one portion to a well-stirred suspension of pyridinium
chlorochromate (PCC; 815mg) and a trace of NaOAc in abs. CH 2Cl2 (20 ml). The mixture was stirred at r.t.
(2.5h). Then, abs. Et 2O was added and the supernatant liquid decanted from a black tar. The insoluble residue
was washed with abs. Et2O (3Â), the combined org. soln. passed through silica gel (Et2O), and the solvent
evaporated: 5b (576 mg, 95%). White solid. 1H-NMR (300 MHz, CDCl3): 4.08, 3.91 (AB, 2J ˆ 8.6, CH2(17));
2.51 (ddd, 2J ˆ 15.8, 3J(2ax,1ax) ˆ 10.6, 3J(2ax,1eq) ˆ 7.3, HaxÀC(2)); 2.37 (ddd, 2J ˆ 15.8, 3J(2eq,1ax) ˆ 7.2,
3J(2eq,1eq) ˆ 4.2, HeqÀC(2)); 2.24 (dd, 2J ˆ 15.8, 4J(15b,14ax) ˆ 2.2, HbÀC(15)); 2.01 (m, q-like, w1/2 ꢀ 9,
HÀC(13)); 1.95 1.83 ( m, HeqÀC(1), HeqÀC(14)); 1.39, 1.35(2 s, Me2C(O)2)); 1.07 (s, Me(18)); 1.02 (s, Me(20));
0.98 (s, Me(19)).

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3. Ketone 5b from Diol 2 and from Tosylate 3. a) TsCl (22 mg) was added to a soln. of 2 [1] (11.5mg) in abs.
pyridine (2 ml). The mixture was refluxed (18 h). Then H2O was added and the mixture extracted with Et2O.
The org. phase was washed with H2O, dried (MgSO4), and evaporated, and the residue purified by CC (hexane/
AcOEt 1:1): 5b (5.4 mg, 50%) as a white foam and unchanged 2 (5.2 mg, 47%).
b) A soln. of 3 [1] (5mg) in abs. pyridine (4 ml) was refluxed (18 h). Workup and CC as described in a)
gave 5b (3 mg, 89%).
c) A soln. of 3 (5mg) in abs. toluene (4 ml) was refluxed (18 h). Workup and CC as described in a) gave 5b
(3.3 mg, 98%).
d) NaOEt (6 mg) was added to a soln. of 3 (6 mg) in abs. THF (2 ml), and the mixture was stirred at r.t.
(2 h). Workup and prep. TLC (hexane/AcOEt 1:1) gave 5b (2.1 mg, 52%).
e) NaH (80% suspension in oil; 7 mg) was added to a soln. of 3 (6 mg) in abs. THF (2 ml), and the mixture
was stirred at r.t. (2 h). Workup and purification as described in d) gave 5b (2 mg, 49%).
4. (3S,16R)-16,17-(Isopropylidenedioxy)phyllocladan-3-ol 3-(Methanesulfonate) (7) and (3S,16R)-16,17-
(Isopropylidenedioxy(3-2H)phyllocladane-3-ol 3-(Methanesulfonate) (7'). Methanesulfonyl chloride (70 ml)
was added to a soln. of 6 [1] (64 mg) in abs. pyridine (2 ml), and the mixture was kept at r.t. (40 h). Then H2O
was added and the mixture extracted with Et2O. Workup and CC (hexane/AcOEt 5:1) yielded 7 (73 mg, 94%).
White solid. 1H-NMR (300 MHz, CDCl3): 4.34 (m, dd-like, HÀC(3)); 4.05, 3.89 (AB, 2J ˆ 8.6, CH2(17)); 3.00 (s,
MeSO3); 2.23 (dd, 2J ˆ 14.6, 4J(15b,14ax) ˆ 2.1, HbÀC(15)); 1.98 (m, w1/2 ꢀ 8, HÀC(13)); 1.38, 1.34 (2s,
Me2C(O)2); 1.01 (s, Me(18)); 0.90 (s, Me(20)); 0.85( s, Me(19)).
Analogous treatment of 6' [1] (56 mg) afforded 7' (57 mg, 84%). White solid. 1H-NMR (300 MHz, CDCl3):
4.06, 3.89 (AB, 2J ˆ 8.6, CH2(17)); 3.01 (s, MeSO3); 2.23 (dd, 2J ˆ 14.6, 4J(15b,14ax) ˆ 2.1, HbÀC(15)); 1.98 (m,
w1/2 ꢀ 8, HÀC(13)); 1.38, 1.34 (2s, Me2C(O)2); 1.01 (s, Me(18)); 0.90 (s, Me(20)); 0.85( s, Me(19)).
5. (16R)-16,17-(Isopropylidenedioxy)phylloclad-2-ene (8) and (16R)-16,17-(Isopropylidenedioxy)(3-
2H)phylloclad-2-ene (8'). The mixture of 7 (70 mg), LiBr (42 mg), and Li2CO3 (40 mg) in abs. dimethylforma-
mide (2 ml) was refluxed (1 h). Workup and CC (hexane/AcOEt 10 :1) yielded 8 (47 mg, 86%). Clear, colorless
1
needles. IR (CHCl3): 2988, 2937, 2864, 1456, 1381, 1371, 1244, 1176, 1157, 1107, 1052, 1022, 986, 891. H-NMR
(300 MHz, CDCl3): 5.38 (m, 2 H, HÀC(2), HÀC(3)); 4.08, 3.92 (AB, 2J ˆ 8.6, CH2(17)); 2.30 (dd, 2J ˆ 14.5,
4J(15b,14ax) ˆ 2.1, HbÀC(15)); 1.99 (m, w1/2 ꢀ 9, HÀC(13)); 1.89 (ddd, 2J ˆ 11.1, 3J(14eq,13) ˆ 4.8,
4J(14eq,12eq) ˆ 2.5, HeqÀC(14)); 1.39, 1.35(2 s, Me2C(O)2); 0.94 (s, Me(20)); 0.89 (s, Me(19)); 0.86 (s,
‡
‡
‡
‡
Me(18)). CI-MS: 362 (5, [M ‡ NH4] ), 345(15, [ M ‡ H] ), 329 (49, [M À CH3] ), 304 (100, [M À C3H4] ).
Analogous treatment of 7' (56 mg) afforded 8' (40 mg, 92%). White crystals. 1H-NMR (300 MHz, CDCl3):
3
3
2
2
5.38 (dd, J(2,1ax) ˆ 6.0, J(2,1eq) ˆ 1.7, 1 H, HÀC(2)); 4.08, 3.92 (AB, J ˆ 8.6, CH2(17)); 2.30 (dd, J ˆ 14.5,
4J(15b,14ax) ˆ 2.1, HbÀC(15)); 1.99 (m, w1/2 ꢀ 9, HÀC(13)); 1.89 (ddd, 2J ˆ 11.1, 3J(14eq,13) ˆ 4.8,
4J(14eq,12eq) ˆ 2.5, HeqÀC(14)); 1.39, 1.35(2 s, Me2C(O)2); 0.94 (s, Me(20)); 0.89 (s, Me(19)); 0.86 (s,
Me(18)). 13C-NMR (75.4 MHz, CDCl3): 137.6 (t, J (C,D) ˆ 23.5, C(3)); 121.2 (C(2)); 108.4 (Me2C(O)2); 91.6
1
(C(16)); 69.9 (C(17)); 55.1 (C(9)); 52.1 (C(5)); 49.1 (C(14)); 47.7 (C(15)); 44.4 (C(13)); 43.9 (C(8)); 40.4
(C(7)); 40.0 (C(1)); 36.5(C(10)); 33.7 (C(18)); 34.4 (C(4)); 31.9 C(19)); 27.9 (C(12)); 27.0, 26.8 ( Me2C(O)2);
22.9 (C(18)); 21.2 (C(6)); 20.0 (C(11)); 18.4 (C(2)); 15.3 (C(20)).
6. Hydroxy Esters 11, 11', 12, and 12'. NaBH4 (3 mg) was added to a soln. of 9 [1] (9.5mg) in abs. THF
(2 ml) and stirred at r.t. (3 d). Then H2O was added and the soln. extracted with Et2O. The org. phase was
washed with H2O, dried (MgSO4), and evaporated and the residue purified by prep. TLC (toluene/AcOEt 5:2):
(2R,3R,16R)-16,17-(isopropylidenedioxy)phyllocladane-2,3-diol 2-(3-methylbut-2-enoate) (11; 4.9 mg, 51%)
and (2R,3R,16R)-16,17-(isopropylidenedioxy)phyllocladane-2,3-diol 3-(3-methylbut-2-enoate) (12; 2.3 mg,
24%) both as white crystals.
Data of 11 (300 MHz, CDCl3): 5.68 (m, t-like, HÀC(2')); 4.96 (ddd, 3J(2,1ax) ˆ 11.8, 3J(2,3) ˆ 10.1,
3J(2,1eq) ˆ 4.5, HÀC(2)); 4.05, 3.89 (AB, 2J ˆ 8.6, CH2(17)); 3.20 (d, 3J(3,2) ˆ 10.1, HÀC(3)); 2.24 (dd, 2J ˆ
4
4
14.3, J(15b,14ax) ˆ 1.8, HbÀC(15)); 2.17, 1.90 (2d, J(4',2') ˆ 4J(MeÀC(3'),2') ˆ 1.2, Me(4'), MeÀC(3')); 1.38,
1.34 (2s, Me2C(O)2); 1.04 (s, Me(18)); 1.00 (s, Me(20)); 0.86 (s, Me(19)).
Data of 12: (300 MHz, CDCl3): 5.76 (m, t-like, HÀC(2')); 4.51 (d, 3J(3,2) ˆ 0.1, HÀC(3)); 4.07, 3.89 (AB,
2J ˆ 8.6, CH2(17)); 3.80 (ddd, 3J(2,1ax) ˆ 11.8, 3J(3,2) ˆ 10.1, 3J(2,1eq) ˆ 4.5, HÀC(2)); 2.19, 1.92 (2d, 4J(4',2') ˆ
4J(MeÀC(3'),2') ˆ 1.1, Me(4'), MeÀC(3')); 1.38, 1.34 (2s, Me2C(O)2); 0.95( s, Me(18)); 0.89 (s, Me(20)); 0.87 (s,
Me(19)).
Analogous treatment of 9 [1] (75mg) with NaBD 4 (100 mg) in abs. THF (5ml) gave after CC (hexane/
AcOEt 1:1) (2R,3R,16R)-16,17-(isopropylidenedioxy)(3-2H)phyllocladane-2,3-diol 2-(3-methylbut-2-enoate)
(11'; 39 mg, 52%) and (2R,3R,16R)-16,17-(isopropylidenedioxy)(3-2H)phyllocladane-2,3-diol 3-(3-methylbut-2-
enoate) (12', 18 mg, 24%), both as white crystals.

Helvetica Chimica Acta Vol. 86 (2003)
447
Data of 11': 1H-NMR (300 MHz, CDCl3): 5.68 (m, t-like, HÀC(2')); 4.95( dd, 3J(2,1ax) ˆ 11.4, 3J(2,1eq) ˆ
2
2
4
4.6, HÀC(2)); 4.05, 3.90 (AB, J ˆ 8.6, CH2(17)); 2.24 (dd, J ˆ 14.3, J(15b,14ax) ˆ 1.8, HbÀC(15)); 2.17, 1.90
(2d, J(4',5') ˆ 4J(MeÀC(3'),2') ˆ 1.2, Me(4'), MeÀC(3')); 1.38, 1.34 (2s, Me2C(O)2); 1.04 (s, Me(18)); 1.00 (s,
4
Me(20)); 0.86 (s, Me(19)).
Data of 12': 1H-NMR (300 MHz, CDCl3): 5.76 (m, t-like, HÀC(2')); 4.07, 3.89 (AB, 2J ˆ 8.6, CH2(17)); 3.80
(dd, 3J(2,1ax) ˆ 11.8, 3J(2,1eq) ˆ 4.5, HÀC(2)); 2.19, 1.92 (each d, 4J(4',5') ˆ 4J(MeÀC(3'),2') ˆ 1.1, Me(4'),
MeÀC(3')); 1.38, 1.34 (2s, Me2C(O)2); 0.95( s, Me(18)); 0.88 (s, Me(20)); 0.87 (s, Me(19)).
7. (2R,3R,16R)-16,17-(Isopropylidenedioxy)phyllocladane-2,3-diol 2-(4-Methylbenzenesulfonate) (13).
LiAlH4 (50 mg) was added to a soln. of 9 [1] (35mg) in abs. THF (4 ml) and stirred at r.t. (30 min). Then
EtOH and H2O were added followed by some dil. H2SO4 soln. to dissolve the precipitate. The soln. was
extracted with Et2O, the org. phase washed with H2O, dried (MgSO4), and evaporated. The crude residue
(30 mg) was dissolved in abs. pyridine (2 ml). TsCl (40 mg) was added and the mixture kept at r.t. (3 d). Workup
and CC (hexane/AcOEt 1:1) gave 13 (6.5mg, 16%). White foam. 1H-NMR (300 MHz, CDCl3): 7.81, 7.35
3
(AA'BB', J ˆ 8.3, arom. H); 4.63 (ddd, 3J(2,1ax) ˆ 11.6, 3J(2,3) ˆ 9.8, J(2,1eq) ˆ 4.7, HÀC(2)); 4.04, 3.89 (AB,
2J ˆ 8.6, CH2(17)); 3.17 (d, 3J(3,2) ˆ 9.8, HÀC(3)); 2.45( s, MeC6H4); 2.18 (dd, 2J ˆ 14.5, 4J(15b,14ax) ˆ 2.2,
2
3
4
HbÀC(15)); 1.89 (ddd, J ˆ 1.2, J(14eq,13) ˆ 4.8, J(14eq,12eq) ˆ 2.4, HeqÀC(14)); 1.38, 1.34 (2s, Me2C(O)2);
1.02 (s, Me(18)); 0.90 (s, Me(20)); 0.79 (s, Me(19)).
8. (2R,3S,16R)-2,3-Epoxy-16,17-(isopropylidenedioxy)phyllocladane (14) and (2R,3S,16R)-2,3-Epoxy-
16,17-(isopropylidenedioxy)(3-2H)phyllocladane (14'). At À308, 0.1m dimethyldioxirane in acetone [7] (2 ml)
was added to 8 (35mg) in abs. CH 2Cl2 (4 ml), and the mixture was stirred at r.t. (15h). Evaporation and CC
(hexane/AcOEt 10 :1) gave 14 (14 mg, 38%). White needles. IR (CHCl3): 3016, 2988, 2937, 2865, 1456, 1381,
1371, 1244, 1206, 1151, 1052, 891, 826. 1H-NMR (600 MHz, CDCl3): 4.06, 3.90 (AB, 2J ˆ 8.6, CH2(17)); 3.16 (dd,
3
3
2
4
3J(2,1eq) ˆ 6.2, J(2,3) ˆ 3.9, HÀC(2)); 2.78 (d, J(3,2) ˆ 3.9, HÀC(3)); 2.10 (dd, J ˆ 14.5, J(15b,14ax) ˆ 2.1,
2
3
HbÀC(15)); 1.98 (m, w1/2 ꢀ 11, HÀC(13)); 1.92 (dd, J(1eq,1ax) ˆ 14.9, J(1eq,2) ˆ 6.2, HeqÀC(1)); 1.85( ddd,
2J(14eq,14ax) ˆ 11.3, 3J(14eq,13) ˆ 4.8, 4J(14eq,12eq) ˆ 2.4, HeqÀC(14)); 1.68 (m, w1/2 ꢀ 27, HeqÀC(12)); 1.38,
1.34 (2s, Me2C(O)2); 1.08 (s, Me(18)); 0.98 (s, Me(20)); 0.86 (s, Me(19)). 13C-NMR (150.9 MHz, CDCl3): 108.4
(Me2C(O)2); 91.4 (C(16)); 69.8 (C(17)); 61.5 (C(3)); 54.7 (C(9)); 52.3 (C(2)); 48.7 (C(14)); 47.4 (C(15)); 47.1
(C(5)); 44.3 (C(13)); 43.6 (C(8)); 40.2 (C(7)); 39.4 (C(1)); 36.2 (C(10)); 32.5 (C(4)); 28.2 (C(18)); 27.8 (C(12));
‡
27.0, 26.8 (Me2C(O)2); 22.3 (C(19)); 20.4 (C(6)); 19.9 (C(11)); 17.5(C(20)). CI-MS: 378 (23, [ M ‡ NH4] ), 361
‡
‡
‡
(14, [M ‡ H] ), 345(86, [ M À Me] ), 343 (30, [M À OH] ), 320 (45), 285 (100).
Analogous treatment of 13' (30 mg) afforded 14' (12 mg, 38%). White needles. 1H-NMR (300 MHz,
CDCl3): 4.06, 3.90 (AB, 2J ˆ 8.6, CH2(17)); 3.16 (d, 3J(2,1eq) ˆ 6.2, 3J(2,1ax) ꢀ 0, HÀC(2)); 2.10 (dd, 2J ˆ 14.5,
4J(15b,14ax) ˆ 2.1, HbÀC(15)); 1.98 (m, w1/2 ꢀ 11, HÀC(13)); 1.92 (dd, 2J ˆ 4.9, 3J(1eq,2) ˆ 6.2, HeqÀC1)); 1.85
(ddd, 2J ˆ 11.3, 3J(14eq,13) ˆ 4.8, 4J(14eq,12eq) ˆ 2.4, HeqÀC(14)); 1.68 (m, w1/2 ꢀ 27, HeqÀC(12)); 1.38, 1.34 (2s,
Me2C(O)2); 1.08 (s, Me(18)); 0.98 (s, Me(20)); 0.86 (s, Me(19)).
9. (2S,3R,16R)-2,3-Epoxy-16,17-(isopropylidenedioxy)phyllocladane (15). Treatment of 13 (5mg) in abs.
THF (3 ml) with LiAlH4 (30 mg) at r.t. (40 h) gave, after prep. TLC ((hexane/acetone 9 :1), 15 (2 mg, 68%).
Colorless oil that crystallized after several weeks to yield suitable crystals for an X-ray analysis. IR (CHCl3):
2971, 2931, 2856, 1727, 1460, 1370, 1245, 1150, 1050. 1H-NMR (600 MHz, CDCl3): 4.07, 3.91 (AB, 2J ˆ 8.6,
CH2(17)); 3.23 (ddd, 3J(2,1ax) ˆ 4.3, 3J(2,3) ˆ 4.0, 3J(2,1eq) ˆ 2.2, HÀC(2)); 2.83 (d, 3J(3,2) ˆ 4.0, HÀC(3));
2
4
2
3
2.22 (dd, J ˆ 14.5, J(15b,14ax) ˆ 2.2, HbÀC(15)); 2.14 (dd, J ˆ 1 5.0, J(1eq,2) ˆ 2.2, HeqÀC(1)); 1.98 (m, q-
2
3
4
like, w1/2 ꢀ 9, HÀC(13)); 1.86 (ddd, J ˆ 11.2, J(14eq,13) ˆ 4.7, J(14eq,12eq) ˆ 2.4, HeqÀC(14)); 1.37, 1.34 (2s,
Me2C(O)2); 1.06 (s, Me(18)); 1.02 (s, Me(20)); 0.98 (s, Me(19)). 13C-NMR (150.9 MHz, CDCl3): 108.3
(Me2C(O)2); 69.8 (C(17)); 61.0 (C(3)); 56.5 (C(9)); 54.3 (C(2)); 52.2 (C(5)); 49.3 (C(15)); 47.8 (C(14)); 44.2
(C(13)); 40.5(C(7)); 37.8 (C(1)); 30.3 (C(18)); 27.8 (C(12)); 26.8 (2 C, Me2C(O)2); 21.3 (C(6)); 20.6 (C(19));
‡
‡
‡
20.4 (C(11)); 16.5(C(20)). CI-MS: 378 ( < 5 , [M ‡ NH4] ), 345(16, [ M À Me] ), 320 (87, [M À C3H4] ), 302 (6,
.
‡
‡
‡
[M À C3H4 À H2O] ), 285(23, [ M À C3H4 À H2O À CH3] ), 131 (100). EI-MS: 360 (< 5, M ), 345(100, [ M À
‡
Me] ).
10. (1RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]decanes ((Æ)-trans-Decalins ˆ (Æ)-trans-Decahydronaphtha-
lenes) 17 25 and 17' 25'. (1RS,4RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]decan-4-ol (ˆ(2RS,4aRS,8aSR)-Deca-
hydro-1,1,4a-trimethylnaphthalen-2-ol; 17) and (1RS,4RS,6SR)-1,5,5-Trimethyl(4-2H)bicyclo[4.4.0]decan-4-ol
(17'). To a soln. of 16 [8] (4.1 g) in abs. THF (20 ml), LiAlH4 (2 g) was added in portions at 08, and the mixture
was stirred at r.t. (1 h). After workup as described in Exper. 7 the residue was dissolved in abs. EtOH (25ml) and
stirred in the presence of 10% Pd/C (1 g) under a slight H2 pressure at r.t. (15h). Bulb-to-bulb distillation at
1
1508/0.05Torr gave 17 [8a,b][10] (3.14 g, 75%). Viscous, yellowish oil. H-NMR (600 MHz, CDCl3): 3.22 (m,
dd-like, 3J(4,3ax) ꢀ 9, 3J(4,3eq) ꢀ 7, H ÀC(4)); 1.80 (m, HeqÀC(8), OH); 1.62 (m, dt-like, CH2(3); 1.60 (m, dq-

448
Helvetica Chimica Acta Vol. 86 (2003)
like, 2J ˆ 13.5, HeqÀC(7)); 1.42 (br. m, CH2(9)); 1.40 (m, dt-like, HeqÀC(2)), 1.31 (m, dt-like, HeqÀC(10)); 1.25
(m, dt-like, 2J ˆ 13.5, HaxÀC(7)); 1.2 (br. m, HaxÀC(2), HaxÀC(8)); 1.03 (br. m, HaxÀC(10)); 0.96 (s,
MeeqÀC(5)); 0.91 (s, MeÀC(1)); 0.83 (dd, 3J(6,7ax) ˆ 12.0, 3J(6,7eq) ˆ 2.7, HÀC(6)); 0.75( s, MeaxÀC(5)).
13C-NMR (150 MHz, CDCl3): 79.3 (C(4)); 52.7 (C(6)); 45.2 (C(10)); 40.2 (C(2)); 38.8 (C(5)); 34.1 (C(1)); 27.8
(MeeqÀC(5)); 27.6 (C(3)); 27.5 (C(8)); 21.7 (C(9)); 21.6 (C(7)); 19.2 (MeÀC(1)); 15.0 (MeaxÀC(5)). EI-MS:
.
‡
‡
‡
196 (18, M ), 181 (8, [M À CH3] ), 163 (53, [M À CH3 À H2O] ), 83 (100).
Analogous treatment of 16 (2.02 g) with LiAlD4 (1.3 g) afforded 17' (2.06 g, 92%) after bulb-to-bulb
distillation at 1208/0.01 Torr. Clear oil. IR (CHCl3): 3614, 2931, 2850, 1458, 1382, 1366, 1286, 1170, 1132, 1084,
1061, 1040, 1016, 931. 1H-NMR (300 MHz, CDCl3): 1.80 (m, HeqÀC(8), OH); 1.62 (m, CH2(3); 1.60 (m, dq-like,
HeqÀC(7)); 1.42 (m, CH2(9)); 1.40 (m, dt-like, HeqÀC(2)), 1.31 (m, dt-like, HeqÀC(10)); 1.25( m, HaxÀC(7)); 1.2
(m, HaxÀC(2), HaxÀC(8)); 1.03 (m, HaxÀC(10)); 0.95( s, MeeqÀC(5)); 0.91 (s, MeÀC(1)); 0.83 (dd, 3J(6,7ax) ˆ
12.0, 3J(6,7eq) ˆ 2.7, HÀC(6)); 0.75( s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 78.8 (t, 1J (C,D) ˆ 21.4,
C(4)); 52.7 (C(6)); 45.2 (C(10)); 40.2 (C(2)); 38.7 (C(5)); 34.1 (C(1)); 27.7 (MeeqÀC(5)); 27.5 (C(3)); 27.4
.
‡
(C(8)); 21.8 (C(9)); 21.7 (C(7)); 19.2 (Me-C(1)); 15.0 (MeaxÀC(5)). EI-MS: 197 (15, M ), 182 (8, [M À
‡
‡
CH3] ), 164 (42, [M À CH3 À H2O] ), 83 (100).
(1RS,4RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]decan-4-ol Methanesulfonate (ˆ(2RS,4aRS,8aSR)-Decahy-
dro-1,1,4a-trimethylnaphthalen-2-ol Methanesulfonate; 18) and (1RS,4RS,6SR)-1,5,5-Trimethyl(4-2H)bicy-
clo[4.4.0]decan-4-ol Methanesulfonate (18'). Reaction of 17 (3.0 g) in abs. pyridine (25ml) with methanesul-
fonyl chloride (3.5ml) as described in Exper. 4 gave 18 (2.75g, 66%), after CC (hexane/AcOEt 30 :1). Clear
yellowish oil that crystallized after a few days. M.p. 32 358. 1H-NMR (300 MHz, CDCl3): 4.34 (dd, 3J(4,3ax) ˆ
9.5, 3J(4,3eq) ˆ 7.0, HÀC(4)); 3.01 (s, MeSO3); 1.96 (m, td-like, CH2(3)); 1.8 1.0 (m, 11 H); 1.00 (s,
MeeqÀC(5)); 0.95 (s, MeÀC(1)); 0.93 (dd, 3J(6,7ax) ˆ 12.0, 3J(6,7eq) ˆ 2.7, HÀC(6)); 0.84 (s, MeaxÀC(5)).
13C-NMR (75.4 MHz, CDCl3): 90.7 (C(4)); 52.9 (C(6)); 44.8 (C(10)); 39.8 (C(2)); 38.8 (MeSO3); 38.5(C(5));
33.9 (C(1)); 27.9 (MeeqÀC(5)); 27.2, 25.7, 21.6 (C(3), C(8), C(9)); 19.1 (MeÀC(1)); 15.9 (MeaxÀC(5)).
Analogous treatment of 17' (1.93 g) with methanesulfonyl chloride (1.9 ml) afforded 18' (1.80 g, 67%).
Clear oil. IR (CHCl3): 3030, 2976, 2930, 2852, 1460, 1448, 1391, 1383, 1352, 1171, 1122, 1100, 1029, 1012, 970, 912,
850. 1H-NMR (300 MHz, CDCl3): 3.01 (s, MeSO3); 1.96 (m, dd-like, CH2(3)); 1.8 1.0 (m, 11 H); 1.00 (s,
MeeqÀC(5)); 0.95 (s, MeÀC(1)); 0.93 (dd, 3J(6,7ax) ˆ 12.0, 3J(6,7eq) ˆ 2.7, HÀC(6)); 0.84 (s, MeaxÀC(5)).
13C-NMR (75.4 MHz, CDCl3): 90.3 (t, 1J(C,D) ˆ 22.5, C(4)); 52.8 (C(6)); 44.8 (C(10)); 39.8 (C(2)); 38.8
(MeSO3); 38.5(C(5)); 33.9 (C(1)); 27.9 ( MeeqÀC(5)); 27.2, 25.6, 21.6 (C(3), C(8), C(9)); 19.1 ( MeÀC(1)); 15.9
‡
(MeaxÀC(5)). CI-MS: 293 (100, [M ‡ NH4] ).
(1RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]dec-3-ene (ˆ(4aRS,8aSR)-1,2,3,4,4a,5,8,8a-Octahydro-5,5,8a-tri-
methylnaphthalene; 19) and (1RS,6SR)-1,5,5-Trimethyl(4-2H)bicyclo[4.4.0]dec-3-ene (19'). The mixture of 18
(2.75g), LiBr (2.61 g), and Li 2CO3 (2.22 g) in abs. dimethylformamide (20 ml) was refluxed (2 h) and worked
up as described in Exper. 5. The residue was bulb-to-bulb distilled at 1008/0.05Torr: 19 [12] (1.20 g, 67%). Clear
liquid. IR (CHCl3): 3025, 3010, 2929, 2862, 1706, 1655, 1466, 1449, 1377, 1362, 1216, 1212, 1164, 1096, 1012, 987.
1H-NMR (300 MHz, CDCl3): 5.47 (ddd, 3J(3,4) ˆ 10.1, 3J(3,2eq) ˆ 5.8, 3J(3,2ax) ˆ 2.0, HÀC(3)); 5.43 (dd,
3J(4,3) ˆ 10.1, 4J(4,2ax) ˆ 2.7, HÀC(4)); 1.83 (m, dq-like, HeqÀC(7)); 1.79 (br. d, 2J ˆ 16.8, HaxÀC(2)); 1.70 (dd,
2J ˆ 16.8, 3J(2eq,3) ˆ 5.8, HeqÀC(2)); 1.59 (m, dd-like, HeqÀC(9)); 1.50 (m, CH2(8)); 1.43 (m, dq-like,
HeqÀC(10)): 1.30 (m, dd-like, HaxÀC(9)); 1.28 (m, dd-like, HÀC(6)); 1.27 (m, HaxÀC(7)); 1.14 (m, dt-like,
HaxÀC(10)); 0.95( s, MeÀC(1)); 0.93 (s, MeeqÀC(5)); 0.84 (s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 138.3
(C(4)); 121.6 (C(3)); 50.0 (C(6)); 43.7 (C(10)); 41.8 (C(2)); 34.4 (C(5)); 33.0 (C(1)); 31.3 (MeeqÀC(5)); 27.7
.
‡
(C(7)); 22.9 (MeaxÀC(5)); 22.8 (C(9)); 22.3 (C(8)); 19.2 (MeÀC(1)). EI-MS: 178 (18, M ), 163 (100, [M À
‡
CH3] ).
Reaction of 18' (1.70 g) with LiBr (1.78 g) and Li2CO3 (1.44 g) in abs. dimethylformamide (15ml) and CC
(hexane) of the residue gave pure 19' (1.05g, 95%). Clear liquid. IR (CHCl 3): 2929, 2862, 1466, 1448, 1378, 1362,
1048. 1H-NMR (300 MHz, CDCl3): 5.47 (m, w1/2 ꢀ 12, HÀC(3)); 1.83 (m, dq-like, HeqÀC(7)); 1.79 (dd, 2J ˆ
16.8, 3J(2ax,3) ˆ 2.0, HaxÀC(2)); 1.70 (dd, 2J ˆ 16.8, 3J(2eq,3) ˆ 5.8, HeqÀC(2)); 1.59 (m, dd-like, HeqÀC(9));
1.50 (m, CH2(8)); 1.43 (m, dq-like, HeqÀC(10)): 1.30 (m, dd-like, HaxÀC(9)); 1.28 (m, dd-like, HÀC(6)); 1.27
(m, HaxÀC(7)); 1.14 (m, dt-like, HaxÀC(10)); 0.95( s, MeÀC(1)); 0.93 (s, MeeqÀC(5)); 0.84 (s, MeaxÀC(5)).
13C-NMR (75.4 MHz, CDCl3): 138.0 (t, 1J(C,D) ˆ 23.6, C(4)); 121.4 (C(3)); 50.0 (C(6)); 43.7 (C(10)); 41.8
(C(2)); 34.2 (C(5)); 33.0 (C(1)); 31.3 (MeeqÀC(5)); 27.7 (C(7)); 22.9 (MeaxÀC(5)); 22.8 (C(9)); 22.3 (C(8));
.
‡
‡
19.2 (MeÀC(1)). EI-MS: 179 (21, M ), 164 (100, [M À CH3] ), 123 (82).
(1RS,3SR,4RS,6SR)-3,4-Epoxy-1,5,5-trimethylbicyclo[4.4.0]decane (ˆ(1aRS,2aSR,6aRS,7aSR)-Decahy-
dro-2a,7,7-trimethylnaphth[2,3-b]oxirene; 20) and (1RS,3SR,4RS,6SR)-3,4-Epoxy-1,5,5-trimethyl(4-2H)bicy-
clo[4.4.0]decane (20'). At À308, 0.1m dimethyldioxirane in acetone [7] (30 ml) was added to 19 (511 mg) in

Helvetica Chimica Acta Vol. 86 (2003)
449
abs. CH2Cl2 (10 ml) at À308, and the mixture was stirred at r.t. (15h). Evaporation and CC (hexane/AcOEt
30 :1) gave 20 (425mg, 76%). Clear oil with a resinous scent. IR (CHCl 3): 3025, 2932, 2862, 1465, 1448, 1388,
1
1381, 1366, 1237, 1224, 1218, 1210, 1066, 1002, 990, 936, 925, 894, 825, 816. H-NMR (300 MHz, CDCl3): 3.19
(ddd, 3J(3,2eq) ˆ 6.1, 3J(3,4) ˆ 3.9, 3J(3,2ax) ˆ 0.5, HÀC(3)); 2.78 (d, 3J(2,3) ˆ 3.9, HÀC(2)); 1.73 (dd, 2J ˆ 15.1,
3J(2eq,3) ˆ 6.1, HeqÀC(2)); 1.55 1.10 (m, 11 H); 1.07 (s, MeeqÀC(5)); 0.96 (s, MeÀC(1)); 0.92 MeaxÀC(5)).
13C-NMR (75.4 MHz, CDCl3): 62.0 (C(4)); 52.6 (C(3)); 45.1 (C(6)); 44.0 (C(10)); 41.3 (C(2)); 32.8 (C(1)); 32.4
(C(5)); 27.5 (MeeqÀC(5)); 27.3 (C(8)); 22.3 (C(9)); 22.1 (C(7)); 22.0, 21.5 (MeÀC(1), MeaxÀC(5)). EI-MS: 194
.
‡
‡
‡
‡
(5, M ), 179 (63, [M À CH3] ), 161 (83, [M À H2O À CH3] ), 150 (83, [M À C2H4O] ), 95(100).
The analogous reaction of 19' (900 mg) yielded 20' (600 mg, 61%). IR (CHCl3): 2932, 2863, 1448, 1381,
1366, 929. 1H-NMR (300 MHz, CDCl3): 3.19 (dd, 3J(3,2eq) ˆ 6.1, 3J(3,2ax) ˆ 0.5, HÀC(3)); 1.73 (dd, 2J ˆ 15.1,
3J(2eq,3) ˆ 6.1, HeqÀC(2)); 1.55 1.10 (m, 11 H); 1.07 (s, MeeqÀC(5)); 0.96 (s, MeÀC(1)); 0.92 (s, MeaxÀC(5)).
13C-NMR (75.4 MHz, CDCl3): 61.5( t, 1J(C,D) ˆ 26.1, C(4)); 52.6 (C(3)); 45.1 (C(6)); 44.0 (C(10)); 41.3 (C(2));
32.8 (C(1)); 32.4 (C(5)); 27.5 ( MeeqÀC(5)); 27.3 (C(8)); 22.3 (C(9)); 22.1 (C(7)); 22.0, 21.5 ( MeÀC(1),
.
‡
‡
‡
MeaxÀC(5)). EI-MS: 195 (5, M ), 180 (78, [M À CH3] ), 162 (100, [M À H2O À CH3] ), 151 (97, [M À
‡
C2H4O] ).
(1RS,3RS,4RS,6SR)-3-Iodo-1,5,5-trimethylbicyclo[4.4.0]decane-4-ol Acetate (ˆ(2RS,3RS,4aRS,8aSR)-
Decahydro-3-iodo-1,1,4a-trimethylnaphthalen-2-ol Acetate; 21) and (1RS,3RS,4RS,6SR)-3-Iodo-1,5,5-trimeth-
yl(4-2H)bicyclo[4.4.0]decan-4-ol Acetate (21'). Following the procedure of [13], a soln. of 20 (425mg) in abs.
CH2Cl2 (2 ml) was added to the soln. of I2 (610 mg) and PPh3 (630 g) in abs. CH2Cl2 (30 ml), and the mixture was
stirred at r.t. (15h). After evaporation, the residue was dissolved in Ac 2O and filtered over a small amount of
SiO2. Then abs. pyridine (1 ml) was added and the mixture kept at r.t. (2 h). Usual workup and CC (hexane/
AcOEt 30 :1) gave 21 (550 mg, 69%). Yellowish oil that crystallized. M.p. 59 618. IR (CHCl3): 3024, 3016, 2929,
2855, 1727, 1448, 1372, 1248, 1224, 1214, 1101, 1033, 978, 909. 1H-NMR (300 MHz, CDCl3): 5.30 (d, 3J(4,3) ˆ 11.6,
3
3
3
2
3
HÀC(4)); 4.43 (ddd, J(3,2) ˆ 11.6, J(3,2eq) ˆ 10.0, J(3,2ax) ˆ 7.9, HÀC(3)); 2.36 (dd, J ˆ 14.5, J(2eq,3) ˆ
9.8, HeqÀC(2)); 2.20 (dd, 2J ˆ 14.5, 3J(2ax,3) ˆ 7.9, HaxÀC(2)); 2.14 (s, COMe); 1.8 1.0 (m, 9 H); 1.18 (s,
MeeqÀC(5)); 0.93 (s, MeÀC(1)); 0.89 (s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 170.2 (COMe); 78.2
(C(4)); 52.2 (C(6)); 48.2 (C(2)); 45.2 (C(10)); 39.0 (C(5)); 36.7 (C(1)); 27.7 (C(3)); 26.9 (C8)); 24.1, 23.7, 23.1
‡
(MeÀC(1), MeaxÀC(5), MeeqÀC(5)); 22.8, 22.0 (C(7), C(9)); 21.3 (COMe). CI-MS: 382 (100, [M ‡ NH4] ),
‡
‡
322 (10, [M À C2H2O] ), 305(29, [ M À OAc] ).
An analogous treatment of 20' (500 mg) and CC gave 21' (700 mg, 75%). Amber crystals. M.p. 62 648. IR
(CHCl3): 2969, 2934, 2864, 1733, 1469, 1370, 1252, 1162, 1135, 1048, 1029. 1H-NMR (300 MHz, CDCl3): 4.42 (dd,
3J(3,2eq) ˆ 9.8, 3J(3,2ax) ˆ 7.9, HÀC(3)); 2.36 (dd, 2J ˆ 14.5, 3J(2eq,3) ˆ 9.8, HeqÀC(2)); 2.20 (dd, 2J ˆ 14.5,
3J(2ax,3) ˆ 7.9, HaxÀC(2)); 2.14 (s, COMe); 1.8 1.0 (m, 9 H); 1.18 (s, MeeqÀC(5)); 0.93 (s, MeÀC(1)); 0.89 (s,
MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 170.2 (COMe); 77.8 (t, 1J(C,D) ˆ 23.4, C(4)); 52.2 (C(6)); 48.2
(C(2)); 45.2 (C(10)); 39.0 (C(5)); 36.7 (C(1)); 27.7 (C(3)); 26.9 (C(8)); 24.1, 23.7, 23.1 (MeÀC(1), MeaxÀC(5),
‡
‡
MeeqÀC(5)); 22.8, 22.0 (C(7), C(9)); 21.3 (COMe). CI-MS: 383 (100, [M ‡ NH4] ), 323 (6, [M À C2H2O] ),
‡
306 (12, [M À OAc] ).
(1RS,3SR,4RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]decane-3,4-diol 4-Acetate (ˆ(2RS,3SR,4aRS,8aSR)-
Decahydro-1,1,4a-trimethylnaphthalene-2,3-diol 2-Acetate; 22) and (1RS,3SR,4RS,6SR)-1,5,5-Trimethyl(4-
2H)bicyclo[4.4.0]decane-3,4-diol 4-Acetate (22'). According to [14], a soln. of 21 (270 mg) in abs. CH2Cl2
(5ml) was treated with 40% MeCOOOH in AcOH (0.8 ml) at r.t. (15h). After workup and CC (hexane/
AcOEt 5:1), the less-polar fraction contained the 3 a,4a-diol 3a-acetate 23 (25mg, 13%). The main fraction
yielded 22 (85mg, 45%). Colorless amorphous crystals 11). M.p. 127 1298. IR (CHCl3): 3597, 3024, 3016, 2937,
2857, 1720, 1464, 1451, 1375, 1260, 1217, 1211, 1124, 1074, 1044, 984, 975, 950, 913. 1H-NMR (300 MHz, CDCl3):
4.91 (d, 3J(4,3) ˆ 2.9, HÀC(4)); 4.18 (ddd, 3J(3,2ax) ˆ 11.4, 3J(3,2eq) ˆ 5.2, 3J(3,4) ˆ 2.9, HÀC(3)); 2.14 (s,
COMe); 1.86 1.78 (m, 1 H); 1.62 1.03 (m, 10 H); 0.99 (s, MeeqÀC(5); 0.92 (s, MeÀC(1)); 0.86 (s,
MeaxÀC(19)). 13C-NMR (150.9 MHz, CDCl3): 172.2 (COMe); 81.1 (C(4)); 65.5 (C(3)); 47.2 (C(6)); 45.0
(C(10)); 43.4 (C(2)); 38.2 (C(5)); 35.1 (C(1)); 27.6 (MeeqÀC(5)); 27.4 (C(8)); 21.4 (C(9)); 21.3, 21.2 (MeÀC(1),
‡
‡
MeaxÀC(5)); 21.0 (C(7)); 19.9 (COMe). CI-MS: 272 (100, [M ‡ NH4] ), 255 (33, [M ‡ H] ), 237 (9), 212 (20,
‡
[M À C2H2O] ), 195(6).
11
)
TLC of the crude residue showed only one product; acyl migration occurred during CC. Since the target
diols 24 and 24' can be obtained from either isomer, the minor 3a,4a-diol 3a-acetates 23 and 23' are not
described here.

450
Helvetica Chimica Acta Vol. 86 (2003)
Starting from 21' (600 mg), the analogous procedure furnished 23' (45mg, 11%) and 22' (205mg, 49%) as
colorless plates11). M.p. 136 1398 IR (CHCl3): 3598, 3007, 2971, 2936, 2857, 1720, 1464, 1450, 1392, 1371, 1268,
1152, 1100, 1077, 1049, 1026, 1001, 964, 936, 912. 1H-NMR (300 MHz, CDCl3): 4.16 (dd, 3J(2,2ax) ˆ 10.9,
3J(3,2eq) ˆ 5.8, HÀC(3)); 2.13 (s, COMe); 1.86 1.78 (m, 1 H); 1.52 1.15 (m, 10 H); 0.99 (s, MeeqÀC(5)); 0.91
(s, MeÀC(1)); 0.85( s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 171.9 (COMe); 80.7 (t, 1J(C,D) ˆ 23.2, C(4));
65.3 (C(3)); 47.3 (C(6)); 45.0 (C(10)); 43.5 (C(2)); 38.0 (C(5)); 35.1 (C(1)); 27.5 (MeeqÀC(18)); 27.4 (C(8)); 21.4
‡
(C(9)); 21.3, 21.2 (MeÀC(1), MeaxÀC(5)); 21.0 (C(7)); 19.9 (COMe). CI-MS: 273 (100, [M ‡ NH4] ), 256 (24,
‡
‡
[M ‡ H] ), 238 (10), 213 (8, [M À C2H2O] ).
(1RS,3SR,4RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]decane-3,4-diol (ˆ (2RS,3SR,4aRS,8aSR)-Decahydro-
1,1,4a-trimethylnaphthalene-2,3-diol; 24) and (1RS,3SR,4RS,6SR)-1,5,5-trimethyl(4-2H)bicyclo[4.4.0]decane-
3,4-diol (24'). LiAlH4 (25mg) was added to a soln. of 22 (38 mg) in abs. THFat 08 and stirred (1 h).Workup and
CC (hexane/AcOEt 3 :1) afforded 24 (27 mg, 85%). Colorless crystals. M.p. 133 1358. IR (CHCl3): 3566, 3005,
2934, 2855, 1463, 1449, 1384, 1329, 1262, 1237, 1218, 1206, 1191, 114, 1088, 1076, 1030, 986, 953, 932, 912, 900.
1H-NMR (300 MHz, CDCl3): 4.05( ddd, 3J(3,2ax) ˆ 11.3, 3J(3,2eq) ˆ 5.5, 3J(3,4) ˆ 2.9, HÀC(3)); 3.45( d,
3J(4,3) ˆ 2.9, HÀC(4)); 2.12 1.86 (s, w1/2 ꢀ 10, 2 OH); 1.85 1.77 ( m, HeqÀC(7)); 1.53 1.39 (m, 5H); 1.37 1.14
(m, 5H); 0.99 ( s, MeeqÀC(5)); 0.97 (s, MeÀC(1)); 0.83 (s, MeaxÀC(5)). 13C-NMR (150.9 MHz, CDCl3): 79.5
(C(4)); 66.4 (C(3)); 46.0 (C(6)); 45.2 (C(10)); 43.5 (C(2)); 38.3 (C(5)); 35.2 (C(1)); 28.1 (MeeqÀC(5)); 27.6
‡
(C(8)); 21.6 (C(9)); 21.3 (C(7)); 21.3, 20.0 (MeÀC(1), MeaxÀC(5)). CI-MS: 230 (100, [M ‡ NH4] ).
The analogous procedure with 22' (140 mg) gave 24' (106 mg, 91%). Colorless crystals. M.p. 136 1388. IR
(CHCl3): 3571, 3006, 2934, 2854, 1463, 1449, 1406, 1384, 1368, 1296, 1256, 1124, 1056, 1022, 999, 985, 950, 904,
658, 608. 1H-NMR (300 MHz, CDCl3): 4.04 (dd, 3J(3,2ax) ˆ 10.5, 3J(3,2eq) ˆ 5.2, HÀC(3)); 2.38 (s, w1/2 ꢀ 10, 2
OH); 1.85 1.77 ( m, HeqÀC(7)); 1.53 1.39 (m, 5H); 1.37 1.14 ( m, 5H); 0.98 ( s, MeeqÀC(5)); 0.97 (s,
MeÀC(1)); 0.83 (s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 78.9 (t, 1J(C,D) ˆ 22.1, C(4)); 66.2 (C(3)); 45.9
(C(6)); 45.1 (C(10)); 43.4 (C(2)); 38.2 (C(5)); 35.1 (C(1)); 28.0 (MeeqÀC(5)); 27.5(C(8)); 21.5(C(9)); 21.2
‡
(C(7)); 21.1, 19.9 (MeÀC(1), MeaxÀC(5)). CI-MS: 231 (100, [M ‡ NH4] ).
(1RS,3SR,4RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]decane-3,4-diol
3-(4-Methylbenzenesulfonate)
(ˆ(2RS,3SR,4aRS,8aSR)-Decahydro-1,1,4a-trimethylnaphthalene-2,3-diol 3-(4-Methylbenzenesulfonate); 25)
and (1RS,3SR,4RS,6SR)-1,5,5-Trimethyl(4-2H)bicyclo[4.4.0]decane-3,4-diol 3-(4-Methylbenzenesulfonate)
(25'). TsCl (46 mg) was added to a soln. of 24 (20 mg) in abs. pyridine (2 ml), and the mixture was kept at
r.t. (40 h). Then H2O was added and the mixture extracted with Et2O. CC (hexane/AcOEt 5:1) gave 25 (32 mg,
93%). White crystals. M.p. 95 97 8. IR (CHCl3): 3597, 3025, 3016, 2931, 2867, 1599, 1451, 1359, 1292, 1228, 1189,
1176, 1144, 1097, 1051, 991, 942, 929, 915, 902, 837, 815, 672, 666, 664, 603, 588, 555. 1H-NMR (300 MHz, CDCl3):
3
3
7.81, 7.35( AA'BB', J ˆ 8.4, arom. H); 4.90 (1 H, ddd, 3J(3,2ax) ˆ 12.6, J(3,2eq) ˆ 4.5, J(3,4) ˆ 2.6, HÀC(3));
3.51 (d, 3J(4,3) ˆ 2.6, HÀC(4)); 2.45( s, MeC6H4); 1.95 1.85( s, w1/2 ꢀ 4, OH); 1.84 1.73 (m, t-like, 2 H); 1.46
1.15( m, 9 H); 0.95( s, MeeqÀC(5)); 0.89 (s, MeÀC(1)); 0.79 (s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3):
144.7, 134.2 (arom. C); 129.8 (2 C), 127.6 (2 C, arom. CH); 80.1 (C(3)); 77.5(C(4)); 45.5(C(6)); 44.7 (C(10); 40.0
(C(2)); 38.9 (C(5)); 35.5 (C(1)); 27.8 ( MeeqÀC(18)); 27.2 (C(8)); 21.3 (C(9)); 21.5, 21.2, 19.7 (MeÀC(1),
‡
‡
MeaxÀC(5), MeC6H4); 20.9 (C(7)). CI-MS: 384 (100, [M ‡ NH4] ), 230 (59, M ‡ NH4 À TsH] ), 212 (72, [M ‡
‡
‡
NH4 À TsOH] ), 195(17, [ M ‡ H À TsOH] ).
Analogous treatment of 24' (32 mg) gave 25' (53 mg, 96%). White crystals. M.p. 99 1018. IR (CHCl3):
3598, 2968, 2934, 2867, 1599, 1495, 1463, 1450, 1357, 1307, 1176, 1121, 1098, 1045, 1020, 994, 979, 930, 906, 887, 865,
837, 814, 658, 598, 555. 1H-NMR (300 MHz, CDCl3): 7.81, 7.35( AA'BB', J ˆ 8.4, arom. H); 4.90 (dd, 3J(3,2ax) ˆ
12.6, 3J(3,2eq) ˆ 4.5, HÀC(3)); 2.46 (s, MeC6H4); 1.95 1.85( s, w1/2 ꢀ 4, OH); 1.84 1.73 (m, t-like, 2 H); 1.46
1.15( m, 9 H); 0.95( s, MeeqÀC(5)); 0.88 (s, MeÀC(1)); 0.79 (s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3):
144.7, 134.2 (arom. C); 129.8 (2 C), 127.6 (2 C, arom. CH); 80.1 (C(3)); 77.1 (t, 1J(C,D) ˆ 21.9, C(4)); 45.5
(C(6)); 44.7 (C(10)); 40.0 (C(2)); 38.8 (C(5)); 35.5 (C(1)); 27.8 ( MeeqÀC(5)); 27.2 (C(8)); 21.3 (C(9)); 21.6, 21.2,
‡
19.7 (MeÀC(1), MeaxÀC(5), MeC6H4); 20.9 (C(7)). CI-MS: 385(100, [ M ‡ NH4] ), 238 (27), 213 (20, [M ‡
‡
‡
NH4 À TsOH] ), 196 (15, [M ‡ H À TsOH] ).
11. Reactions of the (Æ)-trans-decalins: 25 ! 17, 36 and 25' ! 36', 38. (1RS,3RS,4RS,6SR)-1,5,5-
Trimethyl(3-2H)bicyclo[4.4.0]decan-4-ol (ˆ(2RS,3RS,4aRS,8aSR)-Decahydro-1,1,4a-trimethyl(3-2H)naphtha-
len-2-ol; 38). To a soln. of 25 (50 mg) in abs. THF (4 ml) was added LiAlH4 (50 mg), and the mixture was
stirred at r.t. under N2 (1 h). Workup and CC (hexane/AcOEt 35:1) yielded 17 (23 mg, 86%). Viscous oil.
The analogous treatment of 25' (47 mg) gave 38 (21 mg, 83%). White amorphous solid. M.p. 66 698. IR
(CHCl3): 3614, 2973, 2929, 2852, 1460, 1383, 1248, 1085, 1006, 954. 1H-NMR (600 MHz, CDCl3): 3.22 (m, quint.-
like, 3J(4,3eq) ꢀ 5, 3J(4,D) ꢀ 1.5, HÀC(4)); 1.80 (m, dq-like, 2J ˆ 13.5, HeqÀC(8)); 1.61 (m, t-like, w1/2 ꢀ 10,
HÀC(3)); 1.58 (m, dq-like, 2J ˆ 13.5, HeqÀC(7)); 1.44 (br. m, CH2(9)); 1.40 (dd, 2J ˆ 13, 3J(2eq,3) ˆ 3.5,

Helvetica Chimica Acta Vol. 86 (2003)
451
HeqÀC(2)); 1.29 (m, dq-like, 2J ˆ 13, HeqÀC(10)); 1.25(br. m, dt-like, 2J ˆ 13.5, HaxÀC(7)); 1.18 (br. m, t-like,
HaxÀC(2), HaxÀC(8)); 1.03 (br. m, HaxÀC(10)); 0.96 (s, MeeqÀC(5)); 0.91 (s, MeÀC(1)); 0.83 (dd, 3J(6,7ax) ˆ
12.0, 3J(6,7eq) ˆ 2.7, HÀC(6)); 0.75( s, MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 79.3 (C(4)); 52.6 (C(6));
45.2 (C(10)); 40.1 (C(2)); 38.7 (C(5)); 34.1 (C(1)); 27.7 (MeeqÀC(5)); 27.4 (C(7)); 27.2 (t, 1J(C,D) ˆ 19.5, C(3));
.
‡
‡
21.6 (C(9)); 21.5(C(7)); 19.1 ( MeÀC(1)); 14.9 (MeaxÀC(5)). EI-MS: 197 (27, M ), 182 (13, [M À CH3] ), 164
‡
(71, [M À CH3 À H2O] ), 137 (64), 83 (100).
(1RS,6SR)-1,5,5-Trimethylbicyclo[4.4.0]decan-4-one ( ˆ (4aRS,8aSR)-3,4,4a,5,6,7,8,8a-Octahydro-1,1,4a-
trimethylnaphthalen-2(1H)-one; 36) and (1RS,3RS,6SR)-1,5,5-Trimethyl(3-2H)bicyclo[4.4.0]decan-4-one
(36'). A soln. of 17 (14 mg) in acetone (2 ml) was treated with 2.7m Jones reagent (50 ml) at 08 (5min).
Workup and CC (hexane/AcOEt 30 :1) afforded 36 [8a][10] (11.5mg, 83%). Clear, viscous oil. 1H-NMR
(300 MHz, CDCl3): 2.71 (ddd, 2J ˆ 15.5, 3J(3ax,2ax) ˆ 13.5, J(3ax,2eq) ˆ 6.5, HaxÀC(3)); 2.30 (ddd, 2J ˆ 15.5,
3
3J(3eq,2ax) ˆ 5.2, 3J(3eq,2eq) ˆ 2.9, HeqÀC(3)); 1.83 (m, br. d-like, 1 H); 1.68 (ddd, 2J ˆ 13.3, 3J(2eq,3ax) ˆ 6.5,
3J(2eq,3eq) ˆ 2.9, HeqÀC(2)); 1.6 1.2 (m, 9 H); 1.11 (s, MeeqÀC(5)); 1.06 (s, MeÀC(1)); 1.01 (s, MeaxÀC(5)).
13C-NMR (75.4 MHz, CDCl3): 216.9 (C(4)); 53.5 (C(6)); 47.8 (C(3)); 44.1 (C(10)); 40.8 (C(2)); 35.0 (C(3)); 34.0
(C(1)); 26.9 (C(8)); 25.3 (MeeqÀC(5)); 22.7 (C(9)); 21.7 (C(7)); 21.4 (MeÀC(1)); 18.3 (MeaxÀC(5)). EI-MS:
.
‡
194 (72, M ), 137 (55), 108 (100).
Analogous oxidation of 38 (14 mg) gave 36' (12 mg, 87%). Clear, viscous oil. 1H-NMR (300 MHz, CDCl3):
2.30 (m, quint.-like, 3J(3,2ax) ꢀ 5.2, 3J(3,2eq) ˆ 2.9, 2J(3,D) ꢀ 2.5, HÀC(3)); 1.83 (m, br. d-like, 1 H); 1.68 (dd,
2J ˆ 13.5, 3J(2eq,3) ˆ 2.9, HeqÀC(2)); 1.6 1.2 (m, 9 H); 1.10 (s, MeeqÀC(5)); 1.06 (s, MeÀC(1)); 1.00 (s,
MeaxÀC(5)). 13C-NMR (75.4 MHz, CDCl3): 217.2 (C(4)); 53.5 (C(6)); 47.9 (C(5)); 44.1 (C(10)); 40.7 (C(2)); 34.7
(t, 1J(C,D) ˆ 19.0, C(3)); 34.0 (C(1)); 26.9 (C(8)); 25.3 (MeaxÀC(5)); 22.7 (C(9)); 21.7 (C(7)); 21.3 (MeÀC(1));
.
‡
‡
‡
18.4 (MeaxÀC(5)). EI-MS: 195 (44, M ), 180 (7, [M À CH3] ), 162 (6, [M À CH3 À H2O] ), 137 (36), 108 (100).
Ketones 36 and 36' from Tosylates 25 and 25'. a) A soln. of 25 (5mg) in abs. pyridine (4 ml) was refluxed
(18 h). Then H2O was added and extracted with Et2O. The residue was purified by TLC (hexane/AcOEt 5:1) to
give 36 (4 mg, 87%).
The identical procedure was followed with 25' (3 mg), but only the undeuterated 36 was isolated, and the
expected labelled 36' could not be detected. Since 36 and 36' are not separable by GC, the identification was
.
‡
performed by GC/EI-MS, by which the analysis of the total ion current (TIC) exhibited only m/z 194 (M of
.
‡
36), and no trace of the expected m/z 195( M of 36') could be evidenced. This finding is corroborated by
comparison with pure 36' and its EI-MS that are stored in our GC/MS spectral library12).
b) A soln. of 25 (4 mg) in abs. toluene (4 ml) was refluxed (18 h). Workup and purification as described in
a) gave 36 (3.3 mg, 90%).
The identical thermal reaction was performed with 25' (3 mg) and the product analyzed by GC/MS
according to a). The only product was 36, whereas 36' could not be detected.
c) NaOEt (12 mg) was added to a soln. of 25 (11 mg) in abs. THF (2 ml), and the mixture was stirred at r.t.
(2 h). Workup and purification as described in a) gave 36 (3 mg, 51%). d) NaH (80% suspension in oil; 7 mg)
was added to a soln. of 25 (8 mg) in abs. THF (2 ml), and the mixture was stirred at r.t. (2 h). Workup and
purification as described in a) gave 36 (2 mg, 47%).
The identical reactions c) and d) were performed with 25' (each 4 mg). GC/MS Analysis of the isolated
.
‡
ketones (each 1 mg, 47%) exhibited the presence of both the undeuterated 36 (m/z 194 (M )) and that of the
.
‡
labeled 36' (m/z 195( M )) in the ratio of ca. 6 :1, as calculated from the relative intensities of the individual
TICs.
12. (Æ)-Podocarpa-8,11,13-trienes ((Æ)-trans-1,2,3,4,4a,9,10,10a-Octahydro-1,1,4a-trimethylphenanthrenes)
27 35 and 27' 35'. (3RS)-Podocarpa-8,11,13-trien-3-ol (ˆ (2RS,4aRS,10aSR)-1,2,3,4,4a,9,10,10a-Octahydro-
1,1,4a-trimethylphenanthren-2-ol; 27) and (3RS)-(3-2H)Podocarpa-8,11,13-trien-3-ol (27'). To a soln. of 26 [9]
(2.74 g) in abs. THF (30 ml), LiAlH4 (1.15g) was added in portions at 0 8, and the mixture was stirred at r.t.
(1 h). After workup as described in Exper. 7, the residue was dissolved in abs. EtOH (20 ml) and stirred in the
presence of 10% Pd/C (1 g) under a slight H2 pressure at r.t. (15h). Bulb-to-bulb disitillation at 150 8/0.02 Torr
gave 27 [9b][11] (2.45g, 88%). Clear oil. 1H-NMR (600 MHz, CDCl3): 7.25( d, 3J(11,12) ˆ 7.7, H ÀC(11)); 7.13 (t,
3J(12,11) ˆ 3J(12,13) ˆ 7.7, H ÀC(12)); 7.09 7.05( m, HÀC(13), HÀC(14)); 3.32 (dd, 3J(3,2ax) ˆ 11.4,
2
3
2
3
3J(3,2eq) ˆ 4.7, HÀC(3)); 2.97 (dd, J ˆ 17.1, J(7eq,6ax) ꢀ 6.5, HeqÀC(7)); 2.89 (ddd, J ˆ 17.1, J(7ax,6ax) ˆ
11.5, J(7ax,6eq) ˆ 7.5, H axÀC(7)); 2.33 (dt, J ˆ 13.1, J(1eq,2eq) ˆ 3J(1eq,2ax) ˆ 3.5, HeqÀC(1)); 1.91 (br. m,
ddt-like, HeqÀC(6)); 1.87 1.74 (m, HaxÀC(6), CH2(2)); 1.56 (dt, 2J ˆ 3J(1ax,2ax) ˆ 13.1, 3J(1ax,2eq) ˆ 4.1,
3
2
3
12
)
This shows that there is no significant D-exchange under the GC conditions.

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Helvetica Chimica Acta Vol. 86 (2003)
HaxÀC(1)); 1.34 (dd, 3J(5,6ax) ˆ 12.3, 3J(5,6eq) ˆ 2.2, HÀC(5)); 1.21 (s, Me(17)); 1.09 (s, Me(15)); 0.92 (s,
Me(16)). 13C-NMR (150.9 MHz, CDCl3): 149.6 (C(9)); 135.3 (C(8)); 129.2 (C(14); 126.0 (C(11)); 125.6, 124.7
(C(12), C(13)); 79.0 (C(3)); 50.0 (C(5)); 39.3 (C(4)); 37.9 (C(10)); 37.2 (C(1)); 30.9 (C(7)); 28.4 (C(15)); 28.3
.
‡
‡
(C(2)); 25.1 (C(17)); 19.1 (C(6)); 15.6 (C(16)). EI-MS: 244 (29, M ), 229 (31, [M À CH3] ), 211 (100, [M À
‡
CH3 À H2O] ).
Analogous treatment of 26 (1.02 g) with LiAlD4 (0.5g) afforded 27' (916 mg, 88%), after bulb-to-bulb
distillation at 1508/0.02 Torr. White crystals. M.p. 84 868. IR (CHCl3): 3614, 3007, 2969, 2868, 1488, 1456, 1388,
1378, 1248, 1135, 1098, 1066, 1042, 932. 1H-NMR (300 MHz, CDCl3): 7.24 (m, HÀC(11)); 7.13 6.98 (m,
HÀC(12), HÀC(13), HÀC(14)); 2.94, 2.87 (AB of ABMX, CH2(7)); 2.33 (dt, 2J ˆ 13.0, 3J(1eq,2eq) ˆ
3J(1eq,2ax) ˆ 3.5, HeqÀC(1)); 1.91 (br. m, HeqÀC(6)); 1.87 1.72 (m, HaxÀC(6), CH2(2)); 1.56 (td,
2J(1ax,1eq) ˆ 3J(1ax,2ax) ˆ 3.0, 3J(1ax,2eq) ˆ 4.1, HaxÀC(1)); 1.31 (dd, 3J(5,6ax)ˆ 12.0, 3J(5,6eq)ˆ 2.4,
HÀC(5)); 1.18 (s, Me(17)); 1.06 (s, Me(15)); 0.89 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 149.6 (C(9));
135.3 (C(8)); 129.2 (C(14)); 126.0 (C(11)); 125.6, 124.7 (C(12), (C(13)); 78.4 (t, 1J(C,D) ˆ 21.3, C(3)); 50.0
(C(5)); 39.3 (C(4)); 37.9 (C(10)); 37.2 (C(1)); 30.9 (C(7)); 28.4 (C(15)); 28.3 (C(2)); 25.1 (C(17)); 19.1 (C(6));
.
‡
‡
‡
15.6 (C(16)). EI-MS: 245 (31, M ), 230 (33, [M À CH3] ), 212 (100, [M À CH3 À H2O] ).
(3RS)-Podocarpa-8,11,13-trien-3-ol Methanesulfonate (ˆ (2RS,4aRS,10aSR)-1,2,3,4,4a,9,10,10a-Octahy-
dro-1,1,4a-trimethylphenanthren-2-ol Methanesulfonate; 28) and (3RS)-(3-2H)Podocarpa-8,11,13-trien-3-ol
Methanesulfonate (28'). Reaction of 27 (2.45g) in abs. pyridine (20 ml) with methanesulfonyl chloride (2 ml)
as described in Exper. 4 gave 28 (1.73 g, 54%), after CC (hexane/AcOEt 30 :1 ! 15:1). Clear yellowish oil that
crystallized after a few days. M.p. 107 1098 (from hexane). IR (CHCl3): 3008, 2973, 1489, 1478, 1448, 1356,
1
1332, 1172, 1043, 971, 958, 942, 917, 882, 843. H-NMR (300 MHz, CDCl3): 7.23 7.01 (m, arom. H); 4.39 (dd,
3J(3,2ax) ˆ 11.5, J(3,2eq) ˆ 5.3, HÀC(3)); 3.02 (s, MeSO3); 2.95, 2.88 (AB of ABMX, CH2(7)); 2.36 (dt, J ˆ
13.4, 3J(1eq,2eq) ˆ 3J(1eq,2ax) ˆ 3.6, HeqÀC(1)); 2.16 2.05( m, 2 H); 1.91 1.71 (m, 2 H); 1.5 8 t(d, 2J ˆ
3J(1ax,2ax) ˆ 13.4, 3J(1ax,2eq) ˆ 3.6, HaxÀC(1)); 1.41 (ddd, 3J(5,6ax) ˆ 12.0, 3J(5,6eq) ˆ 2.6, 4J(5,17) ˆ 0.5,
HÀC(5)); 1.22 (d, 4J(17,5) ˆ 0.5, Me(17)); 1.11 (s, Me(15)); 0.98 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3):
148.4 (C(9)); 134.7 (C(8)); 129.0 (C(14)); 125.9 (C(11)); 125.7, 124.3 (C(12), C(13)); 89.9 (C(3)); 50.0 (C(5));
38.8 (MeSO3); 38.7 (C(4)); 37.3 (C(10)); 36.5(C(1)); 30.4 (C(7)); 28.3 (C(15)); 25.9 (C(2)); 24.8 (C(17)); 18.9
3
2
‡
‡
(C(6)); 16.2 (C(16)). CI-MS: 340 (100, [M ‡ NH4] ), 227 (85, [M ‡ H À MsOH] ).
Analogous treatment of 27' (913 mg) with methanesulfonyl chloride (0.8 ml) afforded 28' (650 mg, 54%).
Clear yellowish oil that crystallized after a few days. M.p. 133 1358 (from acetone). IR (CHCl3): 3008, 2973,
1489, 1478, 1448, 1392, 1380, 1353, 1332, 1176, 1133, 1088, 1068, 1044, 1023, 970, 912, 849. 1H-NMR (300 MHz,
CDCl3): 7.23 7.02 (m, arom. H); 3.03 (s, MeSO3); 2.95, 2.88 (AB of ABMX, CH2(7)); 2.36 (dt, 2J ˆ 13.4,
3J(1eq,2eq) ˆ 3J(1eq,2ax) ˆ 3.6, HeqÀC(1)); 2.18 2.08 (m, 2 H); 1.91 1.71 (m, 2 H); 1.5 8 (td, 2J ˆ 3J(ax,2ax) ˆ
13.4, 3J(1ax,2eq) ˆ 3.6, HaxÀC(1)); 1.41 (ddd, 3J(5,6ax) ˆ 12.0, 3J(5,6eq) ˆ 2.6, 4J(5,17) ˆ 0.5, HÀC(5)); 1.22 (d,
4J(17,5) ˆ 0.5, Me(17)); 1.11 (s, Me(15)); 0.98 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 148.4 (C(9)); 134.7
(C(8)); 129.0 (C(14)); 125.9 (C(11)); 125.6, 124.3 (C(12), C(13)); 89.4 (t, 1J(C,D) ˆ 22.4, C(3)); 50.0 (C(5)); 38.8
(MeSO3); 38.6 (C(4)); 37.3 (C(10)); 36.5(C(1)); 30.4 (C(7)); 28.2 C(15)); 25.9 (C(2)); 24.8 (C(17)); 18.8 (C(6));
‡
‡
16.2 (C(16)). CI-MS: 341 (100, [M ‡ NH4] ), 228 (85, [M ‡ H À MsOH] ).
(Æ)-Podocarpa-2,8,11,13-tetraene (ˆ (4aRS,10aRS)-1,4,4a,9,10,10a-Hexahydro-1,1,4a-trimethylphenan-
threne; 29) and (Æ)-(3-2H)-Podocarpa-2,8,11,13-tetraene (29'). The mixture of 28 (1.73 g), LiBr (1.40 g), and
Li2CO3 (1.2 g) in abs. dimethylformamide (20 ml) was refluxed (2 h) and worked up as described in Exper. 5.
The residue was bulb-to-bulb distilled at 1408/0.03 mbar: 29 [11] (960 mg, 79%). Clear liquid. IR (CHCl3): 3008,
1
2962, 2840, 1488, 1470, 1448, 1434, 1374, 1362, 1044. H-NMR (300 MHz, CDCl3): 7.28 7.25( m, 1 arom. H);
7.18 7.01 (m, 3 arom. H); 5.60 (ddd, 3J(2,3) ˆ 10.1, 3J(2,1eq) ˆ 6.0, 3J(2,1ax) ˆ 1.8, HÀC(2)); 5.48 (dd, 3J(3,2) ˆ
10.1, 4J(3,1ax) ˆ 2.7, HÀC(3)); 2.89, 2.86 (AB of ABMX, CH2(7)); 2.53 (dd, 2J ˆ 16.8, 3J(1eq,2) ˆ 6.0,
HeqÀC(1)); 2.11 (br. d, 2J ˆ 16.8, HaxÀC(1)); 1.89 1.63 (m, HÀC(5), CH2(6)); 1.25( d, 4J(17,5) ˆ 0.8, Me(17));
1.04 (s, Me(15)); 0.99 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 147.9 (C(9)); 138.1 (C(3)); 135.4 (C(8)); 128.9
(C(14)); 126.0 (C(11)); 125.9, 125.2 (C(12), C(13)); 121.9 (C(2)); 48.1 (C(5)); 39.8 (C(1)); 37.0 (C(10)); 35.1
.
‡
(C(4)); 31.9 (C(15)); 31.2 (C(7)); 25.3 (C(17)); 22.4 (C(16)); 19.9 (C(6)). EI-MS: 226 (8, M ), 211 (10, [M À
‡
CH3] ), 144 (100).
Reaction of 28' (640 mg) with LiBr (525 mg) and Li2CO3 (440 mg) in abs. dimethylformamide (15ml) and
distillation as above gave pure 29' (400 mg, 89%). Clear liquid. IR (CHCl3): 3008, 2962, 2840, 1488, 1470, 1447,
1434, 1386, 1374, 1362, 1051, 1041, 680, 555. 1H-NMR (300 MHz, CDCl3): 7.28 7.25( m, 1 arom. H); 7.18 7.01
(m, 3 arom. H); 5.59 (dd, 3J(2,1eq) ˆ 6.0, 3J(2,1ax) ˆ 1.5, HÀC(2)); 2.89, 2.86 (AB of ABMX, CH2(7)); 2.53 (dd,
2J ˆ 16.8, 3J(1eq,2) ˆ 6.0, HeqÀC(1)); 2.11 (dd, 2J ˆ 16.8, 3J(1ax,2) ˆ 1.5, HaxÀC(1)); 1.88 1.62 (m, HÀC(5),
CH2(6)); 1.25( d, 4J(17,5) ˆ 0.8, Me(17)); 1.04 (s, Me(15)); 0.98 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 147.9

Helvetica Chimica Acta Vol. 86 (2003)
453
(C(9)); 137.7 (t, 1J(C,D) ˆ 23.6, C(3)); 135.4 (C(8)); 128.9 (C(14)); 126.0 (C(11)); 125.9, 125.3 (C(12), C(13));
121.7 (C(2)); 48.0 (C(5)); 39.7 (C(1)); 37.0 (C(10)); 35.0 (C(4)); 31.8 (C(15)); 31.2 (C(7)); 25.3 (C(17)); 22.4
.
‡
‡
(C(16)); 19.9 (C(6)). EI-MS: 227 (7, M )), 212 (13, [M À CH3] ), 144 (100), 129 (41).
(2RS,3SR)-2,3-Epoxypodocarpa-8,11,13-triene (ˆ (6aRS,7aSR,8aRS,9aSR)-5,6,6a,7,7a,8a,9,9a-Octahydro-
7,7,9a-trimethylphenanthro[2,3-b]oxirene; 30) and (2RS,3SR)-2,3-Epoxy-(3-2H)podocarpa-8,11,13-triene (30').
A soln. of 1m dimethyldioxirane in acetone [7] (7 ml) was added to 29 (106 mg) in abs. CH2Cl2 (2 ml) at À308,
and the mixture was stirred at r.t. (15h). Evaporation and CC of the residue (hexane/AcOEt 30 :1) gave 30
(75mg, 66%). Colorless crystals 13). M.p. 95 97 8. IR (CHCl3): 3007, 2968, 2870, 2842, 1489, 1474, 1436, 1390,
1377, 1366, 1045, 101, 989, 946, 826. 1H-NMR (300 MHz, CDCl3): 7.24 - 6.99 (m, arom. H); 3.36 (ddd, 3J(2,1eq) ˆ
6.3, 3J(2,3) ˆ 3.8, 3J(2,1ax) ˆ 0.5, HÀC(2)); 2.88 (d, 3J(3,2) ˆ 3.8, HÀC(3)); 2.83, 2.77 (AB of ABMX, CH2(7));
2.57 (dd, 2J ˆ 14.8, 3J(1eq,2) ˆ 6.3, HeqÀC(1)); 1.82 1.76 (m, HaxÀC(1), HeqÀC(6)); 1.65 1.50 ( m, ddd-like,
HaxÀC(6)); 1.42 (ddd, 3J(5,6ax) ˆ 12.4, 3J(5,6eq) ˆ 1.7, 4J(5,17) ˆ 1.1, HÀC(5)); 1.24 (d, 4J(17,5) ˆ 1.1, Me(17)),
1.18 (s, Me(15)), 1.09 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 146.9 (C(9)); 135.5 (C(8)); 128.8 (C(14));
126.0 (2 C), 125.4 (C(11), C(12), C(13)); 61.2 (C(3)); 52.8 (C(2)); 43.5 (C(5)); 39.3 (C(1)); 36.8 (C(10)); 33.0
.
‡
(C(4)); 31.5(C(7)); 28.0 (C(15)); 27.4 (C(17)); 21.8 (C(16)); 19.4 (C(6)). EI-MS: 242 (28,
CH3] ), 209 (55, [M À H2O À CH3] ).
M
), 227 (100, M À
‡
‡
The analogous reaction of 29' (290 mg) yielded 30' (210 mg, 68%)13). Colorless crystals. M.p. 94 968. IR
(CHCl3): 3007, 2968, 2209, 1490, 1412, 1390, 1378, 1366, 1126, 1046, 1009, 928, 874, 555. 1H-NMR (300 MHz,
CDCl3): 7.24 6.99 (m, arom. H); 3.35( dd, 3J(2,1eq) ˆ 6.3, 3J(2,1ax) ˆ 0.5, HÀC(2)); 2.83, 2.77 (AB of ABMX,
2
3
CH2(7)); 2.57 (dd, J ˆ 14.8, J(1eq,2) ˆ 6.3, HeqÀC(1)); 1.82 1.75( m, HaxÀC(1), HeqÀC(6)); 1.65 1.50 ( m,
ddd-like, HaxÀC(6)); 1.42 (ddd, 3J(5,6ax) ˆ 12.4, 3J(5,6eq) ˆ 1.8, 4J(5,17) ˆ 1.1, HÀC(5)); 1.24 (d, 4J(17,5) ˆ 1.1,
Me(17)); 1.18 (s, Me(15)); 1.09 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 146.9 (C(9)); 135.4 (C(8)); 128.8
(C(14)); 126.0 (2 C), 125.4 (C(11), C(12), C(13)); 60.8 (t, 1J(C,D) ˆ 26.2, C(3)); 52.6 (C(2)); 43.5 (C(5)); 39.2
(C(1)); 36.7 (C(10)); 32.8 (C(4)); 31.4 (C(7)); 28.0 (C(15)); 27.4 (C(17)); 21.7 (C(16)); 19.3 (C(6)). EI-MS: 243
.
‡
‡
‡
(39, M ), 228 (100, [M À CH3] ), 210 (63, [M À H2O À CH3] ), 129 (53).
(2RS,3RS)-2-Iodopodocarpa-8,11,13-trien-3-ol Acetate (ˆ (2RS,3RS,4aRS,10aSR)-1,2,3,4,4a,9,10,10a-Oc-
tahydro-3-iodo-1,1,4a-trimethylphenanthren-2-ol Acetate; 31) and (2RS,3RS)-2-Iodo(3-2H)podocarpa-8,11,13-
trien-3-ol Acetate (31'). According to [13], a soln. of 30 (25mg) in abs. CH 2Cl2 (1 ml) was added to the soln. of I2
(29 mg) and PPh3 (30 g) in abs. CH2Cl2 (5ml), and the mixture was stirred at r.t. (15h). After evaporation, the
residue was dissolved in Ac2O, the soln. filtered over a small amount of SiO2, and then, abs. pyridine (0.5ml) was
added and the mixture kept at r.t. (2 h). Usual workup and CC (hexane/AcOEt 30 :1) gave 31 (36 mg, 85%).
Clear colorless crystals. M.p. 169 1718. IR (CHCl3): 3008, 2970, 2945, 2870, 1737, 1490, 1469, 1449, 1434, 1396,
1372, 1324, 1248, 1082, 1034. 1H-NMR (300 MHz, CDCl3): 7.16 6.98 (m, arom. H); 5.50 (d, 3J(3,2) ˆ 12.2,
HÀC(3)); 4.45( ddd, 3J(2,3) ˆ 12.2, 3J(2,1ax) ˆ 9.9, 3J(2,1eq) ˆ 8.4, HÀC(2)); 3.04 (dd, 2J ˆ 14.3, 3J(1ax,2) ˆ 9.9,
HaxÀC(1)); 2.87 2.78 (m, HeqÀC(1), CH2(7)); 2.16 (s, COMe); 1.78 1.66 (m, HÀC(5), CH2(6)); 1.50 (s,
Me(17)); 1.06 (s, Me(15)); 1.00 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 170.3 (COMe); 148.8 (C(9)); 134.0
(C(8)); 128.7 (C(14)); 126.6 (C(11)); 126.4, 125.7 (C(12), C(13)); 77.5 (C(3)); 51.6 (C(1)); 46.2 (C(5)); 40.3
(C(10)); 39.0 (C(4)); 31.0 (C(7)); 30.8 (C(17)); 27.7 (C(2)); 24.3 (C(16)); 23.0 (C(15)); 21.4 (COMe); 17.1
‡
‡
‡
(C(6)). CI-MS: 430 (100, [M ‡ NH4] ), 370 (7, [M À C2H2O] ), 353 (25, [M ‡ H À AcOH] ), 225(63, [ M ‡
‡
H À AcOH À I] ), 130 (100).
An analogous treatment of 30' (180 mg) and CC gave 31' (250 mg, 82%). Colorless amorphous crystals.
M.p. 157 1618. IR (CHCl3): 2970, 1737, 1490, 1469, 1449, 1370, 1248, 1137, 1090, 1030. 1H-NMR (300 MHz,
CDCl3): 7.20 6.98 (m, arom. H); 4.45( t, 3J(2,1ax) ˆ 3J(2,1eq) ˆ 9.9, HÀC(2)); 3.04 (dd, 2J ˆ 4.2, 3J(1ax,2) ˆ 9.9,
HaxÀC(1)); 2.93 2.70 (m, HeqÀC(1), H2C(7)); 2.16 (s, COMe); 1.78 1.68 (m, H-C(5), CH2(6)); 1.50 (s,
Me(17)); 1.05( s, Me(15)); 1.00 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 170.2 (COMe); 148.7 (C(9)); 133.9
(C(8)); 128.6 (C(14); 126.5(C(11)); 126.3, 125.6 (C(12), C(13)); 77.1 ( t, 1J(C,D) ˆ 23.5, C(3)); 51.5 (C(1)); 46.1
(C(5)); 40.2 (C(10)); 38.8 (C(4)); 30.8 (C(7)); 30.7 (C(17)); 27.5 (C(2)); 24.2 (C(16)); 22.9 (C(15)); 21.3
‡
‡
‡
(COMe); 20.0 (C(6)). CI-MS: 431 (96, [M ‡ NH4] ), 371 (5, [M À C2H2O] ), 354 (38, [M ‡ H À AcOH] ), 226
‡
(63, [M ‡ H À AcOH À I] ), 131 (100).
(2RS,3SR)-Podocarpa-8,11,13-triene-2,3-diol 3-Acetate (ˆ (2RS,3SR,4aRS,10aSR)-1,2,3,4,4a,9,10,10a-Oc-
tahydro-1,1,4a-trimethylphenanthrene-2,3-diol 2-Acetate; 32) and (2RS,3RS)-(3-2H)Podocarpa-8,11,13-triene-
2,3-diol 3-Acetate (32'). A soln. of 31 (320 mg) in abs. CH2Cl2 (6 ml) was treated with 40% MeCOOOH in
13
)
The less-polar minor fraction contained the 2b,3b-epoxy derivative (6%). The compound is not described
here.

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Helvetica Chimica Acta Vol. 86 (2003)
ACOH (1 ml) at r.t. (15h) [14]. Workup and CC (hexane/AcOEt 10 :1 ! 3 :1) gave 32 (100 mg, 43%).
Brownish oil that crystallized after standing for several days14). M.p. 159 1628. IR (CHCl3): 3598, 3008, 2970,
1722, 1489, 1447, 1376, 1248, 1045, 981, 958, 908, 620, 556. 1H-NMR (300 MHz, CDCl3): 7.29 7.06 (m, arom. H);
4.99 (d, 3J(3,2) ˆ 2.8, HÀC(3)); 4.32 (ddd, 3J(2,1ax) ˆ 12.2, 3J(2,1eq) ˆ 4.3, 3J(2,3) ˆ 2.8, HÀC(2)); 2.97, 2.94
(AB of ABMX, CH2(7)); 2.36 (m, dd-like, 2J ˆ 12.2, 3J(1eq,2) ˆ 4.3, HeqÀC(1)); 2.05( s, COMe); 1.88 1.71 (m,
HaxÀC(1), HÀC(5), CH2(6)); 1.24 (d, 4J(17,5) ˆ 0.5, Me(17)); 1.07 (s, Me(15)), 0.97 (s, Me(16)). 13C-NMR
(75.4 MHz, CDCl3): 172.0 (COMe); 148.8 (C(9)); 134.6 (C(8)); 129.1 (C(14); 125.8 (C(11)); 125.6, 123.9 (C(12),
C(13)); 80.4 (C(3)); 66.0 (C(2)); 43.9 (C(5)); 40.2 (C(1)); 38.7 (C(10)); 38.1 (C(4)); 29.7 (C(7)); 27.8 (C(15));
‡
‡
25.5 (C(17)); 21.6 (C(16)); 20.9 (COMe); 18.1 (C(6)). CI-MS: 320 (100, [M ‡ NH4] ), 303 (20, [M ‡ H] ), 285
‡
‡
‡
(36, [M ‡ H À H2O] ), 227 (34, [M ‡ H À CH3 À AcOH] ), 225(41, [ M ‡ H À AcOH À H2O] ).
Starting from 31' (115mg), the analogous procedure furnished 32' (40 mg, 47%). White crystalline
powder14). M.p. 154 1578. IR (CHCl3): 3598, 3008, 2970, 1722, 1489, 1372, 1263, 1172, 1135, 1052, 1027, 936.
1H-NMR (300 MHz, CDCl3): 7.29 7.06 (m, arom. H); 4.32 (dd, 3J(2,1ax) ˆ 2.2, 3J(2,1eq) ˆ 4.3, HÀC(2)); 2.97,
2
3
2.94 (AB of ABMX, CH2(7)); 2.36 (dd, J ˆ 12.2, J(1eq,2) ˆ 4.3, HeqÀC(1)); 2.05( s, COMe); 1.88 1.71 (m,
HaxÀC(1), HÀC(5), CHC(6)); 1.24 (d, 4J(17,5) ˆ 0.5, Me(17)); 1.07 (s, Me(15)); 0.97 (s, Me(16)). 13C-NMR
(75.4 MHz, CDCl3): 172.0 (COMe); 148.8 (C(9)); 134.6 (C(8)); 129.1 (C(14)); 125.9 (C(11)); 125.6, 123.9
1
(C(12), C(13)); 80.1 (t, J(C,D) ˆ 23.2, C(3)); 66.1 (C(2)); 43.9 (C(5)); 40.1 (C(1)); 38.7 (C(4)); 38.0 (C(10));
‡
29.7 (C(7)); 27.8 (C(15)); 25.5 (C(17)); 21.6 (C(16)); 20.9 (CO Me); 18.1 (C(6)). CI-MS: 321 (100, [M ‡ NH4] ),
‡
‡
‡
304 (18, [M ‡ H] ), 286 (5, [M ‡ H À H2O] ), 228 (10, [M ‡ H À CH3 À AcOH] ), 226 (12, [M ‡ H À
‡
AcOH À H2O] ).
(2RS,3SR)-Podocarpa-8,11,13-triene-2,3-diol (ˆ (2RS,3SR,4aRS,10aSR)-1,2,3,4,4a,9,10,10a-Octahydro-
1,1,4a-trimethylphenanthrene-2,3-diol; 34) and (2RS,3SR)-(3-2H)-Podocarpa-8,11,13-triene-2,3-diol (34').
LiAlH4 (40 mg) was added to a soln. of 32 (60 mg) in abs. THF at 08 and stirred (1 h). Workup and CC
(hexane/AcOEt 5:1) afforded 34 (39 mg, 76%). White crystals. M.p. 150 1548. IR (CHCl3): 3568, 2966, 1734,
1
1602, 1489, 1474, 1381, 1249, 1150, 1102, 1038, 990, 943, 921, 884, 822, 619, 556. H-NMR (300 MHz, CDCl3):
7.26 7.01 (m, arom. H); 4.15( ddd, 3J(2,1ax) ˆ 12.2, 3J(2,1eq) ˆ 4.4, 3J(2,3) ˆ 2.9, HÀC(2)); 3.50 (d, 3J(3,2) ˆ 2.9,
HÀC(3)); 2.97, 2.94 (AB of ABMX, CH2(7)); 2.28 (m, HeqÀC(1), 2 OH); 1.87 1.68 (m, HaxÀC(1), HÀC(5),
CH2(6)); 1.21 (s, Me(17)); 1.08 (s, Me(15)); 0.96 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 148.9 (C(9)); 134.7
(C(8)); 129.0 (C(14)); 125.7 (C(11)); 125.4, 123.9 (C(12), C(13)); 78.7 (C(3)); 66.9 (C(2)); 42.6 (C(5)); 40.0
(C(1)); 38.7 (C(4)); 38.2 (C(10)); 29.9 (C(7)); 28.2 (C(15)); 25.5 (C(17)); 21.6 (C(16)); 18.2 (C(6)). EI-MS: 260
.
‡
‡
‡
(29, M ), 245(20, [ M À CH3] ), 227 (100, [M À CH3 À H2O] ).
The analogous procedure with 32' (22 mg) gave 34' (14 mg, 74%). White crystals. M.p. 147 1508. IR
(CHCl3): 3568, 3007, 2967, 1488, 1448, 1380, 1248, 1134, 1052, 1022, 940, 888. 1H-NMR (300 MHz, CDCl3): 7.27
7.01 (m, arom. H); 4.16 (dd, 3J(2,1ax) ˆ 12.2, 3J(2,1eq) ˆ 4.5, HÀC(2)); 2.97, 2.94 (AB of ABMX, CH2(7)); 2.28
(dd, 2J ˆ 12.2, 3J(1eq,2) ˆ 4.5, HeqÀC(1)); 2.11 (br. s, w1/2 ꢀ 5, OH); 1.87 1.68 (m, HaxÀC(1), HÀC(5),
H2C(6)); 1.21 (s, Me(17)); 1.08 (s, Me(15)); 0.96 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 148.9 (C(9)); 134.7
(C(8)); 129.0 (C(14); 125.7 (C(11)); 125.4, 123.9 (C(12), C(13)); 78.2 (t, 1J(C,D) ˆ 21.9, C(3)); 66.8 (C(2)); 42.6
(C(5)); 40.0 (C(1)); 38.7 (C(4)); 38.1 (C(10)); 29.9 (C(7)); 28.2 (C(15)); 25.5 (C(17)); 21.6 (C(16)); 18.2 (C(6)).
.
‡
‡
‡
EI-MS: 261 (27, M ), 246 (18, [M À CH3] ), 228 (100, [M À CH3 À H2O] ).
(2RS,3SR)-Podocarpa-8,11,13-triene-2,3-diol 2-(4-Methylbenzenesulfonate) (ˆ (2RS,3SR,4aRS,10aSR)-
1,2,3,4,4a,9,10,10a-Octahydro-1,1,4a-trimethylphenanthrene-2,3-diol 3-(4-Methylbenzenesulfonate); 35) and
(2RS,3SR)-(3-2H)Podocarpa-8,11,13-triene-2,3-diol 2-(4-Methylbenzenesulfonate) (35'). TsCl (40 mg) was
added to a soln. of 34 (15mg) in abs. pyridine (1 ml), and the mixture was kept at r.t. (40 h). Then H 2O was
added and the mixture extracted with Et2O. CC (hexane/AcOEt 10 :1) gave 35 (18 mg, 74%). Colorless oil that
crystallyzed after several days. M.p. 139 1418. IR (CHCl3): 3608, 2969, 1599, 1490, 1362, 1176, 1098, 1050, 996,
1
935, 900, 838, 815, 605, 557. H-NMR (300 MHz, CDCl3): 7.87, 7.40 (AA'XX', J ˆ 8.2, arom. H); 7.12 7.00 (m,
3
3
3
3
arom. H); 5.03 (ddd, J(2,1ax) ˆ 10.2, J(2,1eq) ˆ 6.3, J(2,3) ˆ 2.4, HÀC(2)); 3.57 (d, J(3,2) ˆ 2.4, HÀC(3));
2.92, 2.88 (AB of ABMX, CH2(7)); 2.49 (s, MeC6H4); 2.15 2.09 ( m, HeqÀC(1), OH); 1.79 1.64 (m, HaxÀC(1),
HÀC(5), CH2(6)); 1.14 (s, Me(17)); 1.06 (s, Me(15)); 0.93 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 148.1
(C(9)); 144.9 (arom. C); 134.6 (C(8)), 134.2 (arom. C); 129.9 (2 arom. CH); 129.0 (C(14)); 127.7 (2 arom. CH);
125.7 (C(11)); 125.4, 123.9 (C(12), C(13)); 80.5 (C(2)); 76.6 (C(3)); 42.6 (C(5)); 39.0 (C(10)); 38.7 (C(4)); 36.8
(C(1)); 29.6 (C(7)); 28.0 (C(15)); 25.3 (C(17)); 21.6, 21.5 (C(16), MeC6H4); 18.0 (C(6)). CI-MS: 432 (95, [M ‡
‡
NH4] ), 260 (100).
14
)
Acyl migration was not observed ( ! 2,3-diol 2-acetates 33 and 33').

Helvetica Chimica Acta Vol. 86 (2003)
455
Analogous treatment of 34' (14 mg) gave 35' (18 mg, 74%). White crystals. M.p. 136 1418. IR (CHCl3):
3605, 3008, 2969, 1599, 1490, 1448, 1395, 1364, 1308, 1176, 1098, 1049, 999, 935, 900, 867, 832, 815, 602, 557.
1H-NMR (300 MHz, CDCl3): 7.87, 7.40 (AA'XX', J ˆ 8.2, arom. H); 7.12 7.00 (m, arom. H); 5.02 (dd,
3J(2,1ax) ˆ 10.4, 3J(2,1eq) ˆ 6.5, HÀC(2)); 2.92, 2.88 (AB of ABMX, CH2(7)); 2.48 (s, MeC6H4); 2.15 2.09 ( m,
HeqÀC(1), OH); 1.81 1.58 (m, HaxÀC(1), HÀC(5), CH2(6)); 1.12 (s, Me(17)); 1.05( s, Me(15)); 0.93 (s,
Me(16)). 13C-NMR (75.4 MHz, CDCl3): 148.1 (C(9)); 144.9 (arom. C); 134.6 (C(8)), 134.2 (arom. C); 129.9 (2
arom. CH); 129.0 (C(14)); 127.7 (2 arom. CH); 125.8 (C(11)); 125.6, 123.5 (C(12), C(13)); 80.5 (C(2)); 76.1 (t,
1J(C,D) ˆ 22.2, C(3)); 42.2 (C(5)); 39.0 (C(10)); 38.7 (C(4)); 36.8 (C(1)); 29.6 (C(7)); 28.0 (C(15)); 25.3
‡
(C(17)); 21.6, 21.5(C(16), MeC6H4); 18.0 (C(6)). CI-MS: 433 (99, [M ‡ NH4] ), 260 (100).
13. Reactions of the (Æ)-Podocarpanes: 35 ! 27, 37 and 35' ! 37', 39). (2RS,3SR)-(2-2H)-Podocarpa-
8,11,13-trien-3-ol (ˆ (2RS,3RS,4aRS,10aSR)-1,2,3,4,4a,9,10,10a-Octahydro-1,1,4a-trimethyl(3-2H)phenanthren-
2-ol; 39). To a soln. of 35 (20 mg) in abs. THF (2 ml) was added LiAlH4 (18 mg), and the mixture was stirred at
r.t. under N2 (1 h). Workup and CC (hexane/AcOEt 10 :1) yielded 27 (10 mg, 85%). Clear oil.
The analogous treatment of 35' (20 mg) gave 39 (10.5mg, 89%). White amorphous powder. M.p. 95 97 8.
IR (CHCl3): 3614, 3007, 2970, 1488, 1378, 1090, 1071, 1030, 938. 1H-NMR (600 MHz, CDCl3): 7.24 (d, 3J(11,12) ˆ
3
7.6, HÀC(11)); 7.12 (t, J(12,11) ˆ 3J(12,13) ˆ 7.6, HÀC(12)); 7.09 7.03 (m, HÀC(13), HÀC(14)); 3.30 (br. d,
3J(3,2eq) ꢀ 4, HÀC(3)); 2.97 (dd, 2J ˆ 17.1, 3J(7eq,6ax) ˆ 6.5, HeqÀC(7)); 2.89 (ddd, 2J ˆ 17.1, 3J(7ax,6ax) ˆ
11.5, 3J(7ax,6eq) ˆ 7.5, H axÀC(7)); 2.32 (dd, 2J ˆ 13.1, 3J(1eq,2) ˆ 3.5, HeqÀC(1)); 1.91 (br. m, ddt-like,
HeqÀC(6)); 1.81 (br. s, w1/2 ꢀ 12, HÀC(2)); 1.76 (dddd, 2J ˆ 13.0, 3J(6ax,5) ˆ 12.2, 3J(6ax,7ax) ˆ 11.5,
3J(6ax,7eq) ˆ 6.5, HaxÀC(6)); 1.55 (br. d, 2J ˆ 13.1, HaxÀC(1)); 1.33 (dd, 3J(5,6ax) ˆ 12.2, 3J(5,6eq) ˆ 2.2,
HÀC(5)); 1.20 (s, Me(17)); 1.08 (s, Me(15)); 0.90 (s, Me(16)). 13C-NMR (150.9 MHz, CDCl3): 149.6 (C(9));
135.2 (C(8)); 129.2 (C(14)); 126.0 (C(11)); 125.6, 124.7 (C(12), C(13)); 78.9 (C(3)); 50.0 (C(5)); 39.3 (C(4));
37.9 (C(10)); 37.1 (C(1)); 30.9 (C(7)); 28.4 (C(15)); 27.9 (t, 1J(C,D) ˆ 19.2, C(2)); 25.1 (C(17)); 19.0 (C(6)); 15.6
.
‡
‡
‡
(C(16)). EI-MS: 245(27, M ), 230 (25, [M À CH3] ), 212 (100, [M À CH3 À H2O] ).
( Æ )-Podocarpa-8,11,13-trien-3-one (ˆ (4aRS,10aSR)-3,4,4a,9,10,10a-Hexahydro-1,1,4a-trimethylphe-
nanthren-2(1H)-one; 37) and (2RS)-(2-2H)Podocarpa-8,11,13-trien-3-one (37'). A soln. of 27 (15mg) in
acetone (1 ml) was treated with 2.7m Jones reagent (50 ml) at 08 (10 min). Workup and CC (hexane/AcOEt
1
30 :1) afforded 37 [9] (13 mg, 87%). White crystals. M.p. 88 918. H-NMR (300 MHz, CDCl3): 7.27 7.04 (m,
arom. H); 2.95, 2.91 (AB of ABMX, CH2(7)); 2.71 (ddd, 2J ˆ 15.6, 3J(2ax,1ax) ˆ 10.0, 3J(2ax,1eq) ˆ 7.4,
HaxÀC(2)); 2.59 (ddd, 2J ˆ 15.6, 3J(2eq,1ax) ˆ 7.5, 3J(2eq,1eq) ˆ 4.1, HeqÀC(2)); 2.49 (ddd, 2J ˆ 13.1,
3J(1eq,2ax) ˆ 7.4, 3J(1eq,2eq) ˆ 4.1 HeqÀC(1)); 2.01 1.76 (m, HaxÀC(1), HÀC(5), CH2(6)); 1.30 (d,
4J(17,5) ˆ 0.6, Me(17)); 1.17 (s, Me(15); 1.15 (s, Me(16)). 13C-NMR (75.4 MHz, CDCl3): 217.2 (C(3)); 147.3
(C(9)); 134.9 129.1 (C(14)); 126.1 (C(11)); 125.8, 125.4 (C(12), C(13)); 50.6 (C(5)); 47.4 (C(4)); 37.5 (C(1)); 37.4
.
‡
(C(10)); 34.6 (C(2)); 30.8 (C(7)); 26.9 (C(15)); 24.7 (C(17)); 21.1 (C(16)); 20.2 (C(6)). EI-MS: 242 (49, M ),
‡
227 (36, [M À CH3] ), 185(100), 143 (65), 129 (83).
Analogous oxidation of 39 (10 mg) gave 37' (8.5mg, 86%). White crystals M.p. 90 93 8. IR (CHCl3): 2972,
1699, 1490, 1458, 1386, 1248, 1110, 1042. 1H-NMR (300 MHz, CDCl3): 7.27 7.04 (m, arom. H); 2.95, 2.91 (AB of
ABMX, CH2(7)); 2.57 (m, w1/2 ꢀ 15, HeqÀC(2)); 2.49 (dd, 2J ˆ 13.2, 3J(1eq,2eq) ˆ 4.1 HeqÀC(1)); 2.01 1.76 (m,
HaxÀC(1), HÀC(5), CH2(6)); 1.30 (d, 4J(20,5) ˆ 0.6, Me(17)); 1.17 (s, Me(15)); 1.15 (s, Me(16)). 13C-NMR
(75.4 MHz, CDCl3): 217.2 (C(3)); 147.3 (C(9)); 134.9 (C(8)); 129.1 (C(14)); 126.1 (C(11)); 125.8, 125.4 (C(12),
C(13)); 50.6 (C(5)); 47.4 (C(4)); 37.5 (C(1)); 37.4 (C(10)); 34.3 (t, 1J(C,D) ˆ 19.5, C(2)); 30.8 (C(7)); 26.9
.
‡
‡
(C(15)); 24.7 (C(17)); 21.1 (C(16); 20.2 (C(6)). EI-MS: 243 (64, M ), 228 (47, [M À CH3] ), 186 (71), 185(73),
143 (66), 129 (100).
Ketones 37 and 37' from Tosylates 35 and 35'. a) A soln. of 35 (3 mg) in abs. pyridine (4 ml) was refluxed
(18 h). Then H2O was added and the mixture extracted with Et2O. The residue was purified by TLC (hexane/
AcOEt 4 :1): 37 (1.5mg, 86%).
b) A soln. of 35 (3 mg) in abs. toluene (4 ml) was refluxed (18 h). Workup and purification as described in
a) gave 37 (1.6 mg, 91%).
c) NaOEt (4 mg) was added to a soln. of 35 (3 mg) in abs. THF (2 ml), and the mixture was stirred at r.t.
(2 h). Workup and purification as described in a) gave 37 (1 mg, 57%).
d) NaH (80% suspension in oil; 4 mg) was added to a soln. of 35 (3 mg) in abs. THF (2 ml), and the mixture
was stirred at r.t. (2 h). Workup and purification as described in a) gave 37 (1 mg, 57%).
The identical procedures a) d) were followed with 35', but only the undeuterated ketone 37 was isolated,
whereas the expected 37' could not be detected. Since 37 and 37' are not separable by GC, the identification was
.
‡
performed by GC/EI-MS where the analysis of the TIC only exhibited m/z 242 (M of 37), and no trace of the

456
Helvetica Chimica Acta Vol. 86 (2003)
.
‡
expected m/z 243 (M of 37') could be evidenced. This finding is corroborated by comparison with pure 37' and
its EI-MS that are stored in our GC/MS spectral library12).
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Received August 27, 2002