Synthesis of α-hydroxy and α-oxospiranes through ruthenium(II)-catalyzed ring-closing metathesis

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Synthesis of ꢀ-hydroxy and ꢀ-oxospiranes through ruthenium(II)-

catalyzed ring-closing metathesis

Pompiliu S. Aburel, Christian Rømming, Kuangbiao Ma and Kjell Undheim*

1

Department of Chemistry, University of Oslo, N-0315, Oslo, Norway

Received (in Cambridge, UK) 14th February 2001, Accepted 10th May 2001

First published as an Advance Article on the web 30th May 2001

Eﬃcient methodology for the construction of functionalized spiranes using Ru()-catalyzed ring-closing metathesis

reactions is described. The substrates were appropriately substituted ﬁve-, six- and seven-membered cycloalkanes

which were spiroannulated by ﬁve-, six- and seven-membered rings, respectively. The relative stereochemistry of

selected substituted spiranes has been determined by single crystal X-ray analyses. The X-ray structures formed the

basis for NMR correlations of the relative stereochemistry in the groups of compounds prepared. Relative rates in

oxidation reactions could also be used for stereochemical correlations.

Introduction

In spiranes there is no rotation around the quaternary spiro-

center. As a consequence, spiranes are rather rigid structures

and potentially useful as rigid frameworks for attachment of

functional groups, pharmacophoric groups or coordinating

functions for metal complexation. We have for some time been

engaged in developing methodologies for ready access to func-

tionalized spiranes and have reported on the preparation of

β,βЈ-dioxospiranes and on α,βЈ-dioxospiranes.^1,2For additional

modiﬁcations, we have also reported on carbosubstitutions in

α,αЈ-dioxospiro[4.4]nonanes.³Several methods for the prepar-

ation of spiranes have been described which include palladium

promoted spiroannulations onto carbo- or heterocyclic sub-

strates,⁴cascade reactions,^4,5nickel mediated reactions of

alkynes,⁶radical promoted spiroannulations,⁷spiroannulation

of ketals,⁸rearrangement reactions,⁹rhodium-catalyzed

hydroacylations,¹⁰copper or samarium mediated spiroannula-

tions,^11,12aldol condensations and alkylations,^13,14our Rh()-

carbenoid insertion reactions,^1,2Ru()-eﬀected spirocycle

assembly,¹⁵Ru()-catalyzed spiroannulations of dihydropyr-

Scheme 1

azines to form heterocyclic spiranes,¹⁶and in construction of

silaspiranes.¹⁷Considerable eﬀorts recently have been directed

prepared from 2-oxocycloalkane-1-carboxylates 1 (Scheme 1).

towards stereoselective syntheses.^14,18,19

These were metalated and allylated to the quaternary carbon

derivatives 2. The keto group was protected as an ethylene

acetal in structures 3 before LAH reduction of the ester function

to furnish the alcohols 4. These were oxidized in high yields

by pyridinium chlorochromate (PCC) in methylene dichloride

at ambient temperature to the corresponding carbaldehydes

5 which were converted into alcohols by Grignard reagents

(Scheme 2).

The stereochemistry of the adducts formed from the Grignard

reagents and the carbonyl group was strongly aﬀected by the

ring size of the substrates 5 and by the nature of the Grignard

reagent (Scheme 2). With the cyclopentane derivative 5a and

vinylmagnesium chloride, rapid adduct formation at 0 ЊC gave

the alcohol epimers 6a and 6b in the ratio 8 : 1, whereas the

isomer ratios with the larger allyl bromide and butenyl bromide

Grignard reagents were 1 : 4 and 1 : 2, respectively. The isomers

in the pair 8a–8b were separated by ﬂash chromatography.

The other isomer pairs were not separated. The stereochemical

preferences were diﬀerent in the cyclohexane 5b substrate

series. With the vinyl Grignard reagent only the 9a isomer was

isolated. With the cycloheptane substrates the same preferred

stereochemical course gave the isomer 12a. With the allyl

Our previous constructions of β,βЈ-dioxo- and α,βЈ-dioxo-

spiranes were based on rhodium()-carbenoid C–H insertion

reactions for spiroannulation.^1,2The ring sizes in the substrates

could be varied but the spiroannulation was limited to the

addition of ﬁve-membered carbocycles. In this work we report

on the spiroannulation of ﬁve- to seven-membered rings using

bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride

[Ru()] catalyzed ring-closing metathesis (RCM) reactions. The

Grubbs Ru()-catalyst systems have become very important

tools in synthetic organic chemistry.^20,21We have on several

occasions applied these tools to the construction of heterocyclic

rings and heterocyclic spiranes.¹⁶In this work the substrates

used for the formation of α,αЈ-dioxospiranes were appro-

priately functionalized ﬁve- to seven-membered carbocyclic

1,1-dienes. Five- to seven-membered rings were formed in the

spiroannulation reactions.

Results and discussion

The ﬁve-, six- and seven-membered ring substrates for the RCM

eﬀected spirane constructions shown in Schemes 4 and 5 were

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J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

This journal is © The Royal Society of Chemistry 2001

DOI: 10.1039/b101462p

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Scheme 2 Reagents and conditions: (i) (a) n = 0, X = Cl, THF, 0 ЊC, 10 min; (b) n = 1, X = Br, Et₂O, 0 ЊC, 2 h; (c) n = 2, X = Br, THF, 0 ЊC, 6 h.

Scheme 3 Reaction conditions: (i) 15 (2.5 h), 16 (3 h), 17 (9 h); (ii) 18 (6 h), 19 (4 h), 20 (10 h); (iii) 21 (5 h), 22 (7 h), 23 (9 h).

Grignard reagent formation of the isomer pair 10a–10b corre-

sponds to the ﬁnding in the ﬁve-membered ring series 7a–7b

(1 : 4). From the cycloheptane substrate 5c, the ratio was 1 : 1 in

the epimer pair 13a–13b. With the butenyl Grignard reagent

only the alcohol isomer 11b was isolated from the cyclohexane

substrate 5b. On the other hand, the cycloheptane isomer gave

the alcohol epimers 14a–14b in the ratio 1 : 1. The favoured

stereochemical course is likely to result from the conforma-

tional preferences of the substrates and the accessibility of the

carbonyl group in such conformers. In addition, there will be

interactions with the ether oxygen in the acetal function. But

the great variation in product formation within each ring size

also points to steric interactions with the organic moiety in the

Grignard reagent.

The alcohols from the Grignard reactions were oxidized by

PCC at ambient temperature (Scheme 3). In the cycloheptane

series, the isomer 12a and the epimer pairs 13a–13b and

14a–14b were all oxidized to the corresponding ketones 21–23

in high yields. In the cyclohexane series, the isomers 9a and

11b were converted to the ketones 18 and 20, respectively,

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

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whereas oxidation of the epimer pair 10a–10b resulted in

selective oxidation of only the 10a isomer. The major part

of the other alcohol isomer 10b was recovered. Similar results

were seen in the cyclopentane series in that the isomer pairs

6a–6b and 7a–7b reacted by selective oxidation of the 6a and

7a isomers, respectively, whereas the alcohol epimers 6b and

7b were slowly oxidized and 7b was largely recovered from

the product mixture after the reaction. In accordance with

these ﬁndings the alcohol isomer 8a was converted to the

corresponding ketone 17 in high yield. In the suggested con-

formational illustrations in Scheme 2, the hydroxy group can be

regarded as having a cis or a trans relationship to the acetal

function. The structures 6a–14a, in this respect, have a trans

relationship and structures 6b–14b a cis relationship. The

relative structure assignments correspond to the relative con-

ﬁgurations in the hydroxylated spiranes 24–32 in Scheme 4.

In the oxidations it is the hydroxy group with the cis relation-

ship to the acetal group which is the more diﬃcult to oxidize

The ﬁve- and seven-membered ring structures 24, 26, 27,

29, 30 and 32 were formed at 60–75 ЊC in 68–93% yield. The

reaction time was 4 h. The six-membered ring structures 25,

28 and 31 were formed at 30 ЊC over the course of 30 min in

90–94% yield. The easier formation of the six-membered ring

compared with the ﬁve- and seven-membered rings in RCM

reactions with the Ru()-catalyst was also observed for the

reaction of ketones in Scheme 5.

In Scheme

5 RCM reactions of the corresponding

ketones 15–23 are shown. Toluene was used as solvent

with 5 mol% Ru()-catalyst. Invariably the RCM reaction

gave high yields of the ketospiranes 33–41 from the acyclic

ketones 15–23. The reaction conditions, the temperature

and the reaction time, showed that six-membered ring

formation took place more easily than the formation of other

ring sizes.

1

Besides X-ray analyses (vide infra), H NMR spectroscopy

was used in the assignment of structures to the epimeric

1

(Scheme 3). H NMR spectra show strong H-bonding to the

alcohols. In the H NMR spectra the proton signal from the

acetal oxygen which, when taken together with steric inter-

actions, can be used to rationalize the relative rates of the

isomer reactions. High selectivity in the oxidations can be

achieved, but with longer reaction times or more vigorous

reaction conditions both isomers are oxidized to the ketone.

Some simple oxidation experiments with the hydroxylated

spiranes 24–32 are shown in Scheme 6 (vide infra).

The RCM reactions of the hydroxy series 6–14 were run in

toluene solution at slightly elevated temperatures (Scheme 4)

using 5 mol% of the ruthenium()-catalyst. The catalyst was

added in two portions, one half at a time, to maintain an active

concentration of the catalyst throughout the reaction. All sub-

strates, irrespective of the relative conﬁguration at the alcoholic

carbon, gave high yields of the corresponding spiranes 24–32,

i.e. the alcohol epimer ratios were the same in the substrates and

the products. The progress of the reaction was monitored by

GLC or TLC.

hydroxy group in the trans conﬁguration in the spiroannulated

cyclopentyl derivative 24a was located at 3.20 ppm, in the cis

conﬁguration in 24b at 4.74 ppm. In the corresponding cyclo-

hexane series the proton in the trans-structure 27a is located at

3.10 ppm and in the cycloheptane derivative 30a at 3.09 ppm.

The corresponding values in the spiroannulated cyclohexene

derivatives for the trans series were for 25a at 3.39 ppm, 28a at

4.01 ppm, and for 31a 3.64 ppm, and in the cis series 25b, 28b,

31b the ﬁgures were 3.96, 4.20, and 4.54 ppm, respectively.

Similarly the shift values in the spiroannulated cycloheptane

derivatives assigned trans conﬁgurations 26a, 32a were 3.75

and 3.80 ppm and in the cis series 26b, 29b, and 32b, the values

were 4.17, 4.32 and 4.32 ppm, respectively. The patterns in

either series, when taken together with the X-ray data, allow

assignment of relative conﬁgurations for all the spirane alco-

hols. Since the RCM reaction does not involve the epimeric

alcohol, carbon assignment of the relative structure to the

Scheme 4 Reaction conditions: (i) 24 (70 ЊC, 4 h), 25 (30 ЊC, 0.5 h), 26a (60 ЊC, 4 h), 26b (60 ЊC, 4 h); (ii) 27a (60 ЊC, 4 h), 28 (30 ЊC, 0.5 h), 29b (80 ЊC,

4 h); (iii) 30a (70 ЊC, 2 h), 31 (30 ЊC, 0.5 h), 32 (60 ЊC, 2 h).

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J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

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acyclic alcohols 6–14 follows from the structures of the spirane

alcohols.

results showed clearly that the cis structures were oxidized

signiﬁcantly slower than the trans structures.

Hydrogen bonding and its inﬂuence on the oxidation rates of

epimeric alcohol pairs is shown in Scheme 6. The relative rates

of oxidation were monitored by ¹H NMR or by TLC. The

The relative stereochemistry in the spiroannulated six-

membered ring systems 25 and 28 was established by a single

crystal X-ray analysis of the crystalline p-nitrobenzoates 42

and 44 (Scheme 7, Figs. 1 and 2). The alcohols were originally

Scheme 7

obtained in a non-crystalline state and were therefore converted

to the respective crystalline p-nitrobenzoate esters by simple

acylation. The X-ray data are consistent with the products

assigned the cis conﬁgurations 25b and 28b. In the same

manner, for X-ray analysis the spiroannulated non-crystalline

cycloheptane alcohols 26b and 29b were converted into the

crystalline p-nitrobenzoates 43 and 45 (Figs. 3 and 4). These

assignments in the spirane alcohols also conﬁrm the relative

conﬁgurational assignments in the coresponding acyclic

alcohols before the ring-closing reactions as shown in

Scheme 4.

Experimental

The ¹H NMR spectra were recorded at 200 or 300 MHz and the

¹³C NMR spectra at 50 or 75 MHz unless otherwise speciﬁed.

J values are given in Hz. The mass spectra were recorded at

70 eV under electron impact conditions (EI) and are presented

Scheme 5 Reaction conditions: (i) 33 (70 ЊC, 4 h), 34 (30 ЊC, 0.5 h),

35 (60 ЊC, 4 h); (ii) 36 (75 ЊC, 2 h), 37 (30 ЊC, 0.5 h), 38 (60 ЊC, 4 h);

(iii) 39 (75 ЊC, 4 h), 40 (30 ЊC, 0.5 h), 41 (75 ЊC, 2 h).

Scheme 6 24–32 (0.023 mmol) in 1 ml CH₂Cl₂was added rapidly at ambient temperature to a suspension of pyridinium chlorochromate (0.035

mmol) in 1 ml CH₂Cl₂. The relative rates of oxidation were monitored by TLC.

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

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Fig. 1 The ORTEP plot of compound 42. Ellipsoids are shown at 50%

probability. For clarity only the hydrogen at C(12) is shown.

Fig. 3 The ORTEP plot of compound 44. Ellipsoids are shown at 50%

probability. For clarity only the hydrogen at C(13) is shown.

Fig. 2 The ORTEP plot of compound 43. Ellipsoids are shown at 50%

probability. For clarity only the hydrogen at C(13) is shown.

Fig. 4 The ORTEP plot of compound 45. Ellipsoids are shown at 50%

probability. For clarity only the hydrogen at C(14) is shown.

reﬁned against 6482F², R1 = 0.048, R_w2 = 0.127 for I_o> 2σ(I_o)

and R1 = 0.064, R_w2 = 0.143 for all data.

Crystal data for C₂₀H₂₃NO₆(43): M = 373.39, monoclinic,

as m/z (% rel. int.). Dry THF was distilled over sodium

and benzophenone. Dry dichloromethane was distilled from

calcium hydride under argon. Diethyl ether was dried over

sodium. Toluene was distilled from calcium hydride and

degassed by bubbling argon through. Bis(tricyclohexylphos-

phine)(benzylidene)ruthenium() dichloride was purchased

from Strem Chemicals Inc.

P2₁/c, a = 19.205(2), b = 6.591(1), c = 15.014(2) Å, β =

109.51(1)Њ, V = 1791.3(3) Å³, Z = 4, D_x= 1.385 Mg m^Ϫ3

,

µ = 0.102 mm^Ϫ1, T = 150(2) K, 26933 reﬂections were measured

in the 2θ range 4.5–56.6Њ, R_int= 0.057. 336 Parameters were

reﬁned against 4444F², R1 = 0.044, R_w2 = 0.098 for I_o> 2σ(I_o)

and R1 = 0.069, R_w2 = 0.108 for all data.

X-Ray crystallographic analysis for compounds 42, 43, 44 and 45†

Crystal data for C₂₀H₂₃NO₆(44): M = 373.39, monoclinic,

X-Ray data were collected on a Siemens SMART CCD dif-

fractometer²²using graphite monochromated Mo-Kα radiation

(λ = 0.71073 Å). Data collection method: ω-scan, range 0.6Њ,

crystal to detector distance 5 cm. Data reduction and cell

determination were carried out with the SAINT and XPREP

programs.²²Absorption corrections were applied by the use

of the SADABS program.²³The structures were determined

and reﬁned using the SHELXTL program package.²⁴The

non-hydrogen atoms were reﬁned with anisotropic thermal

parameters; hydrogen positions were found from diﬀerence

Fourier maps and reﬁned with isotropic thermal parameters.

The crystals of compound 45 were in the form of very thin

plates (thickness 0.01 mm and less). The data were thus of poor

quality but suﬃced for the determination of the relative con-

ﬁguration. Crystal data for C₁₉H₂₁NO₆(42): M = 359.37,

monoclinic, P2₁/c, a = 18.811(1), b = 6.993(1), c = 13.717(1) Å,

P2₁/n, a = 6.856(1), b = 12.836(1), c = 20.535(2) Å, β =

96.06(1)Њ, V = 1797.1(3) Å³, Z = 4, D_x= 1.380 Mg m^Ϫ3

,

µ = 0.102 mm^Ϫ1, T = 150(2) K, 38813 reﬂections were measured

in the 2θ range 3.7–71.7Њ, R_int= 0.022. 336 Parameters were

reﬁned against 8006F², R1 = 0.047, R_w2 = 0.124 for I_o> 2σ(I_o)

and R1 = 0.064, R_w2 = 0.136 for all data.

¯

Crystal data for C₂₁H₂₅NO₆(45): M = 387.42, triclinic, P1,

a = 8.321(1), b = 12.541(1), c = 18.952(2) Å, α = 99.02(1),

β = 98.99(1), γ = 102.45(1)Њ, V = 1869.8(3) Å³, Z = 4, D_x=

1.376 Mg m^Ϫ3, µ = 0.101 mm^Ϫ1, T = 150(2) K, 14769 reﬂections

were measured in the 2θ range 3.4–46.5Њ, R_int= 0.089. 706

Parameters were reﬁned against 5348F², R1 = 0.098, R_w2 =

0.287 for I_o> 2σ(I_o) and R1 = 0.130, R_w2 = 0.310 for all data.

Ethyl 2-oxocycloheptane-1-carboxylate 1c

Compound 1c was synthesized as described previously.²⁵

β = 109.12(1)Њ, V = 1704.7(2) Å³, Z = 4, D_x= 1.400 Mg m^Ϫ3

,

µ = 0.105 mm^Ϫ1, T = 150(2) K, 31408 reﬂections were measured

in the 2θ range 6.9–66.3Њ, R_int= 0.039. 332 Parameters were

Ethyl 1-allyl-2-oxocyclopentane-1-carboxylate 2a

A solution of ethyl 2-oxocyclopentane-1-carboxylate (5.5 g,

35.25 mmol) in THF (60 ml) was added dropwise to a solution

of sodium hydride (1.69 g, 38.7 mmol, 55–65% moistened with

† CCDC reference numbers 161066–161069. See http://ww w .rsc.org/

suppdata/p1/b1/b101462p/ for crystallographic ﬁles in .cif or other

electronic format.

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oil) in THF (60 ml). The mixture was stirred at ambient tem-

perature for 1 h before a solution of allyl bromide (4.69 g, 38.77

mmol) in THF (60 ml) was added dropwise over 30 min. The

mixture was left at ambient temperature overnight, the solvent

distilled oﬀ, the residual material redissolved in ethyl acetate

(250 ml) and the solution washed with brine (2 × 50 ml), dried

(MgSO₄) and the product isolated after ﬂash chromatography

using hexane–EtOAc 10 : 1, R_f0.30. The product was a colour-

less oil (5.80 g, 85%). HRMS: M 196.1092. C₁₁H₁₆O₃requires

CH₂O), 1.52–1.81 (5 H, m, 4 × CH₂, 1H from CH₂), 2.02–2.09

(1 H, dd, J 14, 8, CH CH᎐CH ), 2.28–2.38 (1 H, m, from CH ),

᎐

2

2.74–2.81 (1 H, dd, J 14, 7, CH CH᎐CH ), 3.76–3.97 (4 H, m,

᎐

2

OCH₂CH₂O), 4.06–4.13 (2 H, q, J 7, CH₃CH₂O), 4.96–5.06

(2 H, m, CH CH᎐CH ), 5.51–5.63 (1 H, m, CH CH᎐CH );

᎐

2

δ_C(CDCl₃) 14.2 (CH₃CH₂O), 19.2 (CH₂), 30.6 (CH₂), 36.0

(CH₂), 37.9 (CH₂), 58.2 (1-C), 60.3 (CH₃CH₂O), 64.6 and 65.4

(OCH CH O ), 117.7 (CH᎐CH ), 118.7 (2-C), 134.2 (CH᎐CH ),

᎐

2

173.4 (CO₂Et); m/z (EI) 240 (M⁺, 4%), 195 (32), 167 (56), 99

196.1099. ν_max(ﬁlm)/cm^Ϫ13050, 2960, 2890 (C–H), 1740 (C᎐O,

(100), 86 (82), 79 (259), 67 (32), 55 (51).

᎐

ketone), 1710 (CO, ester), 1630 (C᎐C); δ (CDCl ) 1.14–1.19

᎐

H

3

(3 H, t, J 7, CH₃CH₂O), 1.80–1.95 (3 H, m, CH₂, 1 H from

CH ), 2.09–2.40 (4 H, m, 1 H from CH CH᎐CH , 1 H from

Ethyl 1-allyl-2,2-ethylenedioxycyclohexane-1-carboxylate 3b

᎐

2

CH , CH ), 2.54–2.59 (1 H, m, CH CH᎐CH ), 4.03–4.12 (2

Compound 3b was obtained from the ketone 2b following the

procedure described above as a colourless oil (92%), R_f0.28.

HRMS: M 245.1514. C₁₄H₂₂O₄requires 245.1518. ν_max(ﬁlm)/

cm^Ϫ12910, 2860 (C–H), 1720 (CO₂Et); δ_H(CDCl₃) 1.15–1.22

(3 H, t, J 7, CH₃CH₂O), 1.35–1.94 (8 H, m, 4 × CH₂), 2.21–2.32

᎐

2

H, q, J 7, CH CH O), 4.99–5.05 (2 H, m, CH CH᎐CH ),

᎐

3

2

5.54–5.68 (1 H, m, CH CH᎐CH ); δ (CDCl ) 13.9 (CH CH O),

᎐

2

C

3

2

19.3 (CH₂), 31.9 (CH₂), 37.6 (CH₂), 37.9 (CH₂), 59.7 (1-C),

61.3 (CH CH O), 118.8 (CH᎐CH ), 132.9 (CH᎐CH ), 170.7

᎐

3

2

(CO Et), 214.3 (2-C᎐O); m/z (EI) 109 (M⁺, 3%), 168 (35), 151

(1 H, dd, J 14, 8, CH CH᎐CH ), 2.68–2.80 (1 H, dd, J 14, 6.5,

᎐

2

(16), 123 (70), 113 (51), 105 (32), 95 (100), 80 (53).

CH CH᎐CH ), 3.80–3.89 (4 H, m, OCH CH O), 4.02–4.13

᎐

2 2 2 2

(2 H, q, J 7, CH CH O), 4.90–5.02 (2 H, m, CH CH᎐CH ),

᎐

3

2

5.48–5.70 (1 H, m, CH CH᎐CH ); δ (CDCl ) 14.1 (CH CH O),

20.6 (CH₂), 23.0 (CH₂), 29.9 (CH₂), 32.0 (CH₂), 35.9 (CH₂),

᎐

2

C

3

2

Ethyl 1-allyl-2-oxocyclohexane-1-carboxylate 2b

Compound 2b was obtained following the procedure described

above as a colourless oil (89%), R_f0.37. HRMS: M 210.1248.

C₁₂H₁₈O₃requires 210.1255. ν_max(ﬁlm)/cm^Ϫ12910, 2840 (C–H),

54.3 (1-C), 60.2 (CH₃CH₂O), 64.5 and 64.7 (OCH₂CH₂O),

110.6 (2-C), 117.4 (CH᎐CH ), 134.0 (CH᎐CH ), 173.4 (CO Et );

᎐

2

m/z (EI) 254 (M⁺, 12%), 213 (7), 181 (17), 125 (11), 99 (100), 86

1727 (C᎐O, ketone), 1708 (CO, ester), 1625 (C᎐C); δ (CDCl )

(28), 55 (12).

᎐

H

3

1.15–1.19 (3 H, t, J 7, CH₃CH₂O), 1.39–1.93 (5 H, m, 3 × CH₂),

2.21–2.29 (1 H, dd, J 14, 8, CH CH᎐CH ), 2.34–238 (3 H,

᎐

2

Ethyl 1-allyl-2,2-ethylenedioxycycloheptane-1-carboxylate 3c

m, 1 H from CH₂, CH₂), 2.42–2.56 (1 H, dd, J 14, 7,

CH CH᎐CH ), 4.07–4.14 (2 H, q, J 7, CH CH O), 4.92–4.98

Compound 3c was obtained from the ketone 2c following the

procedure described above as a colourless oil (89%), R_f0.28.

HRMS: M 268.1670. C₁₅H₂₄O₄requires 245.1674. ν_max(ﬁlm)/

cm^Ϫ13030, 2910, 2880 (C–H), 1720 (CO Et), 1637 (C᎐C);

᎐

2

3

2

(2 H, m, CH CH᎐CH ), 5.59–5.71 (1 H, m, CH CH᎐CH );

᎐

2

δ_C(CDCl₃) 14.0 (CH₃CH₂O), 22.3 (CH₂), 27.4 (CH₂), 35.6

(CH₂), 39.1 (CH₂), 40.9 (CH₂), 60.7 (1-C), 61.0 (CH₃CH₂O),

᎐

2

118.0 (CH᎐CH ), 133.2 (CH᎐CH ), 171.3 (CO Et), 207.3

δ_H(CDCl₃) 1.17–1.25 (3 H, t, J 7, CH₃CH₂O), 1.38–1.78 (8 H,

m, 4 × CH₂), 1.76–1.84 (1 H, m, from CH₂), 1.98–2.12 (1 H,

᎐

2

(2-C᎐O); m/z (EI) 210 (M⁺, 49%), 192 (17), 165 (35), 137 (100),

᎐

119 (41), 67 (37).

m, from CH ), 2.16–2.27 (1 H, dd, J 14, 6, CH CH᎐CH ), 2.76–

᎐

2 2 2

2.88 (1 H, dd, J 14, 7, CH CH᎐CH ), 3.81–3.93 (4 H, m,

᎐

2

OCH₂CH₂O), 4.05–4.18 (2 H, q, J 7, CH₃CH₂O), 4.92–5.05

(2 H, m, CH CH᎐CH ), 5.56–5.73 (1 H, m, CH CH᎐CH );

Ethyl 1-allyl-2-oxocycloheptane-1-carboxylate 2c

᎐

2

Compound 2c was obtained following the procedure described

above as a colourless oil (83%), R_f0.28. HRMS: M 224.1404.

C₁₃H₂₀O₃requires 224.1412. ν_max(ﬁlm)/cm^Ϫ13045, 2920, 2860

δ_C(CDCl₃) 14.2 (CH₃CH₂O), 22.2 (CH₂), 23.0 (CH₂), 28.9

(CH₂), 32.5 (CH₂), 34.5 (CH₂), 38.9 (CH₂), 57.5 (1-C), 60.1

(CH₃CH₂O), 63.9 and 64.6 (OCH₂CH₂O), 112.9 (2-C), 117.3

(C–H), 1740 (C᎐O, ketone), 1700 (CO, ester); 1638 (C᎐C);

δ_H(CDCl₃) 1.15–1.23 (3 H, t, J 7, CH₃CH₂O), 1.28–1.80 (7 H,

m, 3 × CH₂, 1 H from CH₂), 1.96–2.11 (1 H, m, from CH₂),

(CH᎐CH ), 134.9 (CH᎐CH ), 173.9 (CO Et); m/z (EI) 268

᎐ ᎐

2 2 2

᎐

(M⁺, 14%), 227 (39), 195 (37), 171 (14), 99 (100), 86 (11), 55

(34).

2.24–2.36 (1 H, dd, J 14, 7, CH CH᎐CH ), 2.40–2.43 (1 H, m,

᎐

2

from CH₂), 2.57–2.61 (1 H, m, from CH₂), 2.65–2.72 (1 H, dd,

J 14, 7, CH CH᎐CH ), 4.06–4.17 (2 H, q, J 7, CH CH O), 4.95–

1-Allyl-2,2-ethylenedioxycyclopentane-1-methanol 4a

᎐

2

3

2

5.06 (2 H, m, CH CH᎐CH ), 5.57–5.74 (1 H, m, CH CH᎐CH );

δ_C(CDCl₃) 14.0 (CH₃CH₂O), 24.5 (CH₂), 25.4 (CH₂), 29.8

(CH₂), 31.9 (CH₂), 39.5 (CH₂), 42.0 (CH₂), 61.1 (CH₃CH₂O),

LAH (0.646 g, 17 mmol) was added in ﬁve portions to a

solution of the carboxylic ester 3a (2.4 g, 10 mmol) in dry THF

(40 ml ) at 0 ЊC and the mixture stirred at this temperature for

0.5 h and at ambient temperature for 6 h. Excess LAH was

destroyed with saturated NH₄Cl, the mixture extracted with

ethyl acetate (3 × 25 ml), the combined organic extracts dried

(MgSO₄) and evaporated and the residual material subjected to

ﬂash chromatography using hexane–EtOAc 5 : 1, R_f0.15. The

product (3.71 g, 90%) was a colourless oil. HRMS: M 198.1254.

C₁₁H₁₈O₃requires 198.1255. ν_max(ﬁlm)/cm^Ϫ13506 (OH), 3020,

᎐

2

62.7 (1-C), 118.5 (CH᎐CH ), 133.5 (CH᎐CH ), 171.9 (CO Et),

᎐

2

209.0 (2-C᎐O); m/z (EI) 224 (M⁺, 51%), 195 (5), 151 (89), 150

᎐

(100), 137 (37), 81 (69), 67 (90).

Ethyl 1-allyl-2,2-ethylenedioxycyclopentane-1-carboxylate 3a

A solution of the cyclopentanone 2a (6.0 g, 30.6 mmol), ethyl-

ene glycol (5.7 ml), and toluene-p-sulfonic acid (0.3 g) in

benzene (200 ml) was heated under reﬂux for 11 h using a

Dean–Stark trap. Most of the solvent was then distilled oﬀ,

the residual material poured into 10% NH₄OH (50 ml) and the

mixture extracted with diethyl ether (3 × 50 ml). The combined

ethereal extracts were dried (MgSO₄), the ether distilled oﬀ

and the residual material subjected to ﬂash chromatography

using hexane–EtOAc 8 : 1, R_f0.29. The product (11.5 g, 86%)

was a colourless oil. HRMS: M 240.1363. C₁₃H₂₀O₄requires

240.1361. ν_max(ﬁlm)/cm^Ϫ13050, 2965, 2875 (C–H), 1720

2940, 2860 (C–H), 1625 (C᎐C); δ (CDCl ) 1.47–1.61 (4 H, m,

᎐

H

3

2 × CH₂), 1.67–1.85 (2 H, m, CH₂), 2.04–2.11 (1 H, dd, J 14, 7,

CH CH᎐CH ), 2.24–2.31 (1 H, dd, J 14, 7, CH CH᎐CH ),

᎐

2

2.81–2.86 (1 H, dd, J 8, 5, CH₂OH), 3.36–3.43 (1 H, dd, J 12, 8,

CH₂OH), 3.53–3.58 (1 H, dd, J 12, 8, CH₂OH), 3.82–3.93 (4 H,

m, OCH CH O), 4.96–5.07 (2 H, m, CH CH᎐CH ), 5.70–5.84

᎐

2

(1 H, m, CH CH᎐CH ); δ (CDCl ) 18.8 (CH ), 30.2 (CH ), 34.4

᎐

2

C

3

2

(CH₂), 35.3 (CH₂), 49.6 (1-C), 64.2 and 64.5 (OCH₂CH₂O),

65.6 (CH OH), 117.2 (CH᎐CH ), 120.2 (2-C), 135.3 (CH᎐CH );

᎐

2

m/z (EI) 198 (M⁺, 2%), 167 (20), 157 (7), 139 (5), 125 (8), 113

(CO Et), 1630 (C᎐C); δ (CDCl ) 1.18–1.23 (3 H, t, J 7, CH -

(6), 99 (100), 86 (23), 79 (8).

᎐

2

H

3

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

1463

View Article Online

1-Allyl-2,2-ethylenedioxycyclohexane-1-methanol 4b

(1 H, s, CH᎐O); δ (CDCl ) 20.3 (CH ), 22.9 (CH ), 27.2 (CH ),

᎐

C 3 2 2 2

32.4 (CH₂), 33.5 (CH₂), 56.7 (1-C), 64.5 and 64.7 (OCH₂CH₂O),

Compound 4b was obtained from the carboxylic ester 3b

following the procedure described above as a colourless oil

(86%), R_f0.22. HRMS: M 212.1403. C₁₂H₂₀O₃requires

212.1412. ν_max(ﬁlm)/cm^Ϫ13500 (OH), 2910, 2880 (C–H), 1630

110.5 (2-C), 118.0 (CH᎐CH ), 132.6 (CH᎐CH ), 204.9 (CH᎐O);

᎐

2

m/z (EI) 210 (M⁺, 2%), 182 (24), 139 (25), 125 (16), 99 (100),

86 (53), 67 (15), 55 (22).

(C᎐C); δ (CDCl ) 1.31–1.56 (8 H, m, 4 × CH ), 2.07–2.14 (1 H,

᎐

H

3

2

1-Allyl-2,2-ethylenedioxycycloheptane-1-carbaldehyde 5c

dd, J 14, 8, CH CH᎐CH ), 2.29–2.36 (1 H, dd, J 14, 8,

᎐

2

CH CH᎐CH ), 2.80–2.84 (1 H, dd, J 7, 4, CH OH), 3.27–3.43

(1 H, dd, J 12, 7, CH₂OH), 3.66–3.71 (1 H, dd, J 12, 3,

CH₂OH), 3.71–3.90 (4 H, m, OCH₂CH₂O), 4.94–5.02 (2 H, m,

᎐

2

Compound 5c was obtained from the alcohol 4c following the

procedure described above as a colourless oil (79%), R_f0.34.

HRMS: M 224.1411. C₁₃H₂₀O₃requires 224.1412. ν_max(ﬁlm)/

cm^Ϫ13020, 2915, 2862 (C–H), 1715 (CH᎐O), 1663 (C᎐C);

δ_H(CDCl₃) 1.35–1.75 (9 H, m, 4 × CH₂, 1 H from CH₂), 1.92–

1.97 (1 H, m, 1 H from CH₂), 2.28–2.35 (1 H, dd, J 14, 7,

CH CH᎐CH ), 5.70–5.79 (1 H, m, CH CH᎐CH ); δ (CDCl )

᎐

2

C

3

᎐

20.0 (CH₂), 23.1 (CH₂), 29.4 (CH₂), 30.0 (CH₂), 34.1 (CH₂),

44.3 (1-C), 63.9 and 64.3 (OCH₂CH₂O), 64.9 (CHOH), 113.4

(2-C), 117.4 (CH᎐CH ), 134.3 (CH᎐CH ); m/z (EI) 212 (M⁺,

᎐

2

CH CH᎐CH ), 2.61–2.68 (1 H, dd, J 14, 7, CH CH᎐CH ),

᎐ ᎐

2 2 2 2

8%), 181 (12), 171 (9), 125 (14), 99 (100), 86 (29), 55 (19).

3.85–3.92 (4 H, m, OCH₂CH₂O), 4.97–5.04 (2 H, m, CH₂-

CH᎐CH ), 5.50–5.64 (1 H, m, CH CH᎐CH ), 9.57 (1 H, s,

᎐

2

1-Allyl-2,2-ethylenedioxycycloheptane-1-methanol 4c

CH᎐O); δ (CDCl ) 21.5 (CH ), 21.8 (CH ), 28.1 (CH ), 28.3

᎐

C

3

2

(CH₂), 33.8 (CH₂), 35.6 (CH₂), 59.0 (1-C), 64.0 and 64.3

Compound 4c was obtained from the carboxylic ester 3c

following the procedure described above as a colourless oil

(89%), R_f0.22. HRMS: M 226.1569. C₁₃H₂₂O₃requires

226.1570. ν_max(ﬁlm)/cm^Ϫ13520 (OH), 3060, 2920, 2865 (C–H),

(OCH CH O), 113.5 (2-C), 118.1 (CH᎐CH ), 133.4 (CH᎐CH ),

᎐

2

204.0 (CH᎐O); m/z (EI) 224 (M⁺, 3%), 195 (43), 155 (23), 139

᎐

(42), 99 (100), 86 (11), 67 (10), 55 (14).

1632 (C᎐C); δ (CDCl ) 1.39–1.79 (10 H, m, 5 × CH ), 2.12–

᎐

H

3

2

1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)prop-2-en-1-ol 6a

and 6b

2.19 (1 H, dd, J 14, 8, CH CH᎐CH ), 2.26–2.33 (1 H, dd, J 14,

᎐

2

6, CH CH᎐CH ), 3.16–3.20 (1 H, dd, J 9, 3, CH OH), 3.23–

᎐

2

3.30 (1 H, dd, J 11, 9, CH₂OH), 3.59–3.64 (1 H, dd, J 11, 3,

CH₂OH), 3.86–3.96 (4 H, m, OCH₂CH₂O), 5.01–5.08 (2 H, m,

Vinylmagnesium chloride (3.54 ml, 6.02 mmol, 1.7 M in THF)

was added dropwise to a solution of the carbaldehyde 5a

(0.84 g, 4.3 mmol) in THF (10 ml) under argon at 0 ЊC. The

reaction was stopped after 10 min by the addition of saturated

NH₄Cl solution. The aqueous layer was extracted with CH₂Cl₂

(3 × 30 ml), the combined organic layers dried (MgSO₄) and

evaporated. The residual material was subjected to ﬂash

chromatography using hexane–EtOAc 7 : 1 as eluent, R_f0.26.

The product (6a and 6b 8 : 1; 0.78 g, 81%) was a colourless oil.

HRMS: M 224.1408. C₁₃H₂₀O₃requires 224.1412. ν_max(ﬁlm)/

CH CH᎐CH ), 5.79–5.92 (1 H, m, CH CH᎐CH ); δ (CDCl )

᎐

2

C

3

21.3 (CH₂), 21.4 (CH₂), 28.5 (CH₂), 30.8 (CH₂), 32.4 (CH₂),

35.2 (CH₂), 47.5 (1-C), 63.7 and 63.9 (OCH₂CH₂O), 66.6

(CHOH), 116.2 (2-C), 118.2 (CH᎐CH ), 135.5 (CH᎐CH );

᎐

2

m/z (EI) 226 (M⁺, 8%), 209 (7), 195 (43), 185 (60), 167 (11), 129

(9), 99 (100), 86 (10), 53 (5).

1-Allyl-2,2-ethylenedioxycyclopentane-1-carbaldehyde 5a

cm^Ϫ13490 (OH), 3020, 2960, 2880 (C–H) 1630 (C᎐C);

᎐

A solution of the alcohol 4a (1.26 g, 6.3 mmol) in dichloro-

methane (6 ml) was added rapidly to a suspension of pyridin-

ium chlorochromate (2.04 g, 9.5 mmol) in dichloromethane

(10 ml) at ambient temperature. The reaction mixture became a

clear solution before a precipitate appeared. TLC monitoring

showed that the reaction had gone to completion after 6 h.

The black reaction mixture was diluted with 5 volumes of

anhydrous diethyl ether, the solvent decanted, the black solid

washed twice with ether, the combined ether solutions ﬁltered

through Florisil, the ﬁltrate evaporated and the residual

material subjected to ﬂash chromatography using hexane–

EtOAc 7 : 1, R_f0.29_.The product was a colourless oil (1.02 g,

81%). HRMS: M 196.1098. C₁₁H₁₆O₃requires 196.1099.

δ_H(CDCl₃) 1.41–1.93 (6 H, m, 3 × CH₂), 2.08–22.25 (1 H, dd,

J 14.5, 7, CH CH᎐CH ), 2.28–2.39 (1 H, dd, J 14.5, 8,

᎐

2

CH CH᎐CH ), 3.30–3.44 (1 H, d, J 5, CHOH (6b), d, J 7,

᎐

2

CHOH (6a)), 3.79–3.96 (4 H, m, OCH₂CH₂O), 4.08–4.16 (1 H,

m, CHOH), 4.95–5.29 (4 H, m, 2 × CH᎐CH ), 5.74–6.06 (2 H,

᎐

2

m, 2 × CH᎐CH ); δ (CDCl ) (6a): 18.8 (CH ), 30.5 (CH ), 34.6

᎐

2

C

3

2

(CH₂), 35.8 (CH₂), 51.8 (CH₂), 63.8 and 63.84 (OCH₂CH₂O),

75.7 (CHOH), 115.3 (CH᎐CH ), 117.12 (HC(OH)CH᎐CH ),

᎐

2

120.6 (2-C), 135.5 (CH᎐CH ), 137.8 (HC(OH)CH᎐CH ); (6b):

᎐

2

19.8 (CH₂), 29.7 (CH₂), 36.5 (CH₂), 38.6 (CH₂), 52.3 (1-C), 64.0

and 64.1 (OCH CH O), 75.3 (CHOH), 116.2 (CH᎐CH ),

᎐

2

117.16 (HC(OH)CH᎐CH ), 120.2 (2-C), 136.1 (CH᎐CH ),

᎐

2

137.7 (HC(OH)CH᎐CH ); m/z (EI) 224 (M⁺, 0.5%), 183 (16),

ν_max(ﬁlm)/cm^Ϫ13020, 2940, 2860 (C–H), 1720 (CH᎐O), 1625

2

᎐

167 (32), 139 (16), 124 (11), 112 819), 99 (100), 55 (64).

(C᎐C); δ (CDCl ) 1.53–1.79 (5 H, m, 4 × CH , 1 H from CH ),

᎐

H

3

2

2.13–2.23 (2 H, m, 1 H from CH , 1 H from CH CH᎐CH ),

᎐

2

2.58–2.65 (1 H, dd, J 14, 7, CH CH᎐CH ), 3.80–3.95 (4 H, m,

(1R*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)prop-

᎐

2

OCH CH O), 4.95–5.04 (2 H, m, CH CH᎐CH ), 5.47–5.60

2-en-1-ol 6b

᎐

2

(1 H, m, CH CH᎐CH ), 9.52 (1 H, s, CH᎐O); δ (CDCl ) 19.3

᎐

2

C

3

Compound 6b was isolated as the non-reacted part of the

epimeric alcohol substrate 6a–6b (8 : 1) in an oxidation reaction

for the preparation of the ketone 15 (vide infra). The product

was a colourless oil (4%), R_f0.24. HRMS: M 224.1415.

C₁₃H₂₀O₃requires 224.1412. ν_max(ﬁlm)/cm^Ϫ13495 (OH), 3020,

(CH₂), 27.9 (CH₂), 34.7 (CH₂), 35.5 (CH₂), 60.5 (1-C), 64.7

and 64.9 (OCH CH O), 117.9 (CH᎐CH ), 118.9 (2-C), 133.6

᎐

2

(CH᎐CH ), 203.6 (CH᎐O); m/z (EI) 196 (M⁺, 2%), 167 (10), 139

᎐

2

(42), 125 (22), 108 (16), 99 (100), 86 (30), 79 (27), 67 (55), 55

(81).

2970, 2860 (C–H) 1635 (C᎐C); δ (CDCl ) 1.57–1.94 (6 H, m,

᎐

H

3

3 × CH ), 2.13–2.21 (1 H, m, CH CH᎐CH ), 2.30–2.39 (1 H,

᎐

2

1-Allyl-2,2-ethylenedioxycyclohexane-1-carbaldehyde 5b

dd, J 14.5, 8, CH CH᎐CH ), 3.43–3.45 (1 H, d, J 5, CHOH),

᎐

2

Compound 5b was obtained from the alcohol 4b following the

procedure described above as a colourless oil (89%), R_f0.47.

HRMS: M 210.1263. C₁₂H₁₈O₃requires 210.1255. ν_max(ﬁlm)/

cm^Ϫ12915, 2862 (C–H), 1715 (CH᎐O), 1637 (C᎐C); δ (CDCl )

3.83–3.97 (4 H, m, OCH₂CH₂O), 4.12–4.17 (1 H, m, CHOH),

4.99–5.23 (4 H, m, 2 × CH᎐CH ), 5.79–6.09 (2 H, m,

᎐

2

2 × CH᎐CH ); δ (CDCl ) 19.7 (CH ), 29.6 (CH ), 36.5 (CH ),

᎐

2

C

3

2

38.8 (CH₂), 52.2 (1-C), 64.0 and 64.1 (OCH₂CH₂O), 75.4

(CHOH), 116.5 (CH᎐CH ), 117.2 (HC(OH)CH᎐CH ), 120.2

᎐

H

3

1.35–1.50 (6 H, m, 3 × CH₂), 1.59–1.87 (2 H, m, CH₂), 2.20–

2.28 (1 H, dd, J 14, 6, CH CH᎐CH ), 2.57–2.64 (1 H, dd, J 14,

᎐

2

(2-C), 136.3 (CH᎐CH ), 137.7 (HC(OH)CH᎐CH ); m/z (EI)

᎐

2

8, CH CH᎐CH ), 3.82–3.93 (4 H, m, OCH CH O), 4.92–4.98

(M⁺, 1%), 206 (7), 183 (22), 168 (46), 139 (16), 124 (17), 99

(100), 86 (14), 55 (27).

᎐

2

(2 H, m, CH CH᎐CH ), 5.42–5.48 (1 H, m, CH CH᎐CH ), 9.62

᎐

2

1464

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

View Article Online

1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)but-3-en-1-ol 7a

and 7b

ν_max(ﬁlm)/cm^Ϫ13500 (O–H), 3040, 2955, 2875 (C–H), 1638

(C᎐C); δ (CDCl ) 1.38–1.78 (8 H, m, 4 × CH ), 2.00–2.06 (2 H,

m, CH₂), 2.30–2.41 (2 H, m, CH₂), 3.09–3.11 (1 H, dd, J 4, 1.5,

CHOH), 3.63–3.68 (1 H, ddd, J 10.5, 4, 2, CHOH), 3.83–3.97

᎐

H

3

2

Mg powder (0.35 g, 14.3 mmol) in diethyl ether was stirred

under argon overnight, the ether decanted, diethyl ether (20 ml)

added followed by two small crystals of I₂. The mixture was

stirred for 5 min before a solution of allyl bromide (1.61 g, 12.8

mmol) in diethyl ether (20 ml) was added dropwise at a

suﬃcient rate to maintain slight reﬂux. The mixture was stirred

for 3 h before the Grignard reagent was added to a solution of

the carbaldehyde 5a (1.40 g, 7.14 mmol) in diethyl ether (5 ml)

at 0 ЊC under argon. The reaction was stopped after 3 h by the

addition of a saturated NH₄Cl solution. The layers were separ-

ated and the aqueous layer extracted with diethyl ether (3 × 30

ml), the combined organic layers dried (MgSO₄), evaporated

and the product isolated from the residual material by ﬂash

chromatography using hexane–EtOAc 7 : 1 as eluent, R_f0.20.

The product mixture (7a–7b 1 : 4; 1.47 g, 87%) was a colour-

less oil. HRMS: M 238.1565. C₁₄H₂₂O₃requires 238.1568.

ν_max(ﬁlm)/cm^Ϫ13500 (O–H), 3050, 2965, 2870 (C–H), 1625

(4 H, m, OCH CH O), 4.88–5.03 (4 H, m, 2 × CH᎐CH ), 5.76–

᎐

2

5.89 (2 H, m, 2 × CH᎐CH ); δ (CDCl ) 19.9 (CH ), 30.4 (CH ),

᎐

2

C

3

2

30.8 (CH₂), 30.9 (CH₂), 36.7 (CH₂), 38.9 (CH₂), 52.5 (1-C), 63.9

and 64.1 (OCH CH O), 72.9 (CHOH), 114.3 (CH᎐CH ), 116.7

᎐

2

(CH(OH)(CH ) CH᎐CH ), 120.4 (2-C), 136.5 (CH᎐CH ),

᎐

2

139.1 (CH(OH)(CH ) CH᎐CH ); m/z (EI) 252 (M⁺, 0.7%), 221

᎐

2

(10), 193 (7), 168 (41), 139 (14), 124 (25), 99 (100), 86 (17), 55

(27).

(1R*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)-

pent-4-en-1-ol 8b. A colourless oil (48%), R_f0.30. HRMS: M

252.1729. C₁₅H₂₄O₃requires 252.1725. ν_max(ﬁlm)/cm^Ϫ13504 (O–

H), 3040, 2940, 2885 (C–H), 1630 (C᎐C); δ (CDCl ) 1.37–1.83

᎐

H

3

(8 H, m, 4 × CH ), 1.95–2.08 (1 H, m, from CH CH CH᎐CH ),

᎐

2

2.12–2.19 (1 H, dd, J 14, 7, CH CH᎐CH ), 2.28–2.39 (2 H, m,

᎐

2

1 H from CH CH᎐CH , 1 H from CH CH CH᎐CH ), 3.14–

᎐

2

(C᎐C); δ (CDCl ) 1.22–1.84 (6 H, m, 3 × CH ), 2.00–2.42 (4 H,

᎐

H

3

2

3.16 (1 H, d, J 6, CHOH), 3.55–3.61 (1 H, ddd, J 10, 6, 3,

CHOH), 3.82–3.99 (4 H, m, OCH₂CH₂O), 4.89–5.04 (4 H, m,

m, 2 H from CH CH᎐CH , 2 H from OHCH CH᎐CH ), 3.11–

᎐

2

3.17 (1 H, d, J 3, CHOH (7a), d, J 6, CHOH (7b)), 3.66–3.73

(1 H, m, CHOH), 3.83–4.07 (4 H, m, OCH₂CH₂O), 4.97–5.07

2 × CH᎐CH ), 5.73–5.91 (2 H, m, 2 × CH᎐CH ); δ (CDCl )

᎐

2

C

3

18.8 (CH₂), 30.9 (CH₂), 31.4 (CH₂), 31.5 (CH₂), 34.4 (CH₂),

35.7 (CH₂), 51.7 (1-C), 63.5 and 63.7 (OCH₂CH₂O), 74.4

(4 H, m, CH CH᎐CH , CH(OH)CH CH᎐CH ), 5.80–5.96 (2 H,

᎐

2

m, CH CH᎐CH CH(OH)CH CH᎐CH ); δ_C(CDCl₃) (7a):

᎐

2

(CHOH), 114.4 (CH᎐CH ), 116.9 (CH(OH)(CH ) CH᎐CH ),

᎐

2

19.8 (CH₂), 30.3 (CH₂), 36.3 (CH₂), 36.5 (CH₂), 38.8 (CH₂),

52.4 (1-C), 63.9 and 64.2 (OCH₂CH₂O), 73.1 (CHOH), 116.0

120.8 (2-C), 135.8 (CH᎐CH ), 138.8 (CH(OH)(CH₂)₂-

᎐

2

CH᎐CH ); m/z (EI) 252 (M⁺, 0.3%), 211 (7), 168 (33), 124 (22),

᎐

2

(CH᎐CH ), 116.7 (CH(OH)CH CH᎐CH ), 120.4 (2-C), 136.4

᎐

2

99 (100), 79 (20), 67 (26), 55 (46).

(CH᎐CH ), 136.9 (CH(OH)CH CH᎐CH ); (7b): 18.8 (CH ),

᎐

2

30.9 (CH₂), 34.4 (CH₂), 35.6 (CH₂), 37.0 (CH₂), 51.6 (1-C), 63.8

and 63.7 (OCH CH O), 74.7 (CHOH), 115.8 (CH᎐CH ), 117.0

(1S*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycyclohexan-1-yl)-

prop-2-en-1-ol 9a. Compound 9a was obtained following the

procedure described above from the carbaldehyde 5b and vinyl-

magnesium chloride as a colourless oil (80%), R_f0.39. HRMS:

M 238.1577. C₁₄H₂₂O₃requires 238.1568. ν_max(ﬁlm)/cm^Ϫ13598

᎐

2

(CH(OH)CH CH᎐CH ), 120.7 (2-C), 135.7 (CH᎐CH ), 137.3

᎐

2

(CH(OH)CH CH᎐CH ); m/z (EI) 238 (M⁺, 1.37%), 220 (12),

2

197 (98), 168 (49), 155 (6), 135 (20), 107 (24), 99 (100), 86 (18),

67 (15), 55 (23).

(O–H), 3050, 2935, 2860 (C–H), 1625 (C᎐C); δ (CDCl ) 1.38–

᎐

H

3

1.65 (8 H, m, 4 × CH₂), 2.23–2.31 (1 H, dd, J 15, 7, CH₂-

CH᎐CH ), 2.36–2.43 (1 H, dd, J 15, 7, CH CH᎐CH ), 3.77–

(1R*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)but-3-

᎐

2

en-1-ol 7b

3.79 (1 H, d, J 3, CHOH), 3.85–3.99 (4 H, m, OCH₂CH₂O),

4.36–4.39 (1 H, m, CHOH), 4.90–5.26 (4 H, m, 2 × CH᎐CH ),

᎐

2

Compound 7b was isolated as the non-reacted part of the

epimeric alcohol substrate 7a–7b (1 : 4) in an oxidation reaction

for the preparation of the ketone 16 (vide infra). The product

was a colourless oil (33%), R_f0.25. HRMS: M 238.1570.

C₁₄H₂₂O₃requires 238.1568. ν_max(ﬁlm)/cm^Ϫ13500 (O–H), 3040,

2954, 2894 (C–H), 1635 (C᎐C); δ (CDCl ) 1.55–1.84 (6 H, m,

3 × CH₂), 2.15–2.42 (4 H, m, 2 × CH₂), 3.15–3.17 (1 H, d, J 6,

CHOH), 3.66–3.72 (1 H, ddd, J 10, 6, 2, CHOH), 3.83–3.99

5.82–6.02 (2 H, m, 2 × CH᎐CH ); δ (CDCl ) 20.1 (CH ), 23.1

᎐

2

C

3

2

(CH₂), 30.3 (CH₂), 30.6 (CH₂), 33.5 (CH₂), 46.8 (1-C), 63.2

and 64.8 (OCH₂CH₂O), 75.7 (CHOH), 114.3 (2-C), 115.36

(CH᎐CH₂), 116.2 (HC(OH)CH᎐CH₂), 135.8 (CH᎐CH₂), 137.2

᎐

(HC(OH)CH᎐CH ); m/z (EI) 238 (M⁺, 2%), 197 (17), 182 (51),

᎐

2

᎐

H

3

139 (20), 99 (100), 67 (29), 55 (48).

1-(1-Allyl-2,2-ethylenedioxycyclohexan-1-yl)but-3-en-1-ol 10a

and 10b

(4 H, m, OCH CH O), 4.98–5.09 (4 H, m, 2 × CH᎐CH ), 5.80–

5.96 (2 H, m, 2 × CH᎐CH ); δ (CDCl ) 18.8 (CH ), 30.9 (CH ),

᎐

2

᎐

2

C

3

2

Compounds 10a and 10b were obtained from the carbaldehyde

5b and allyl bromide following the procedure described above

as a colourless oil (1 : 4 mixture) (78%), R_f0.19. HRMS:

M 252.1735. C₁₅H₂₄O₃requires 252.1725. ν_max(ﬁlm)/cm^Ϫ13490

34.4 (CH₂), 35.7 (CH₂), 37.0 (CH₂), 51.6 (1-C), 63.6 and

63.8 (OCH CH O), 74.7 (CHOH), 115.8 (CH᎐CH ), 117.0

᎐

2

(CH(OH)CH CH᎐CH ), 120.7 (2-C), 135.7 (CH᎐CH ), 137.3

᎐

2

(CH(OH)CH CH᎐CH ); m/z (EI) 238 (M⁺, 0.90%), 197 (49),

2

(O–H), 3050, 2920, 2890 (C–H), 1630 (C᎐C); δ (CDCl )

᎐

167 (25), 135 (13), 99 (100), 79 (14), 67 (17), 55 (26).

H

3

1.18–1.70 (8 H, m, 4 × CH₂), 2.14–2.50 (4 H, m, 2 H from

CH CH᎐CH , 2 H from OHCH CH᎐CH ), 3.58–3.63 (1 H, s,

᎐

2

1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)pent-4-en-1-ol 8a

and 8b

CHOH (10a), m, CHOH (10b)), 3.86–3.98 (5 H, m, 1 from

CHOH, 4 from OCH CH O), 4.90–5.03 (4 H, m, CH CH᎐CH ,

᎐

2

The Grignard reagent was prepared following the procedure

described above from Mg (0.29 g, 12.2 mmol) and 4-bromo-

but-1-ene (1.21 g, 8.98 mmol) in THF (12 ml) and added to

a solution of the carbaldehyde 5a (0.8 g, 4 mmol) in THF

(5 ml) under argon at 0 ЊC. The reaction mixture was worked up

as above and the product isolated after ﬂash chromatography

using hexane–EtOAc 7 : 1. The ﬁrst eluted product was 8a

followed by 8b

CH(OH)CH CH᎐CH ), 5.81–5.93 (2 H, m, CH CH᎐CH ,

᎐

2

CH(OH)CH CH᎐CH ); δ (CDCl ) (10b): 20.2 (CH ), 23.0

᎐

2

C

3

2

(CH₂), 30.0 (CH₂), 30.5 (CH₂), 33.4 (CH₂), 36.0 (CH₂), 46.5

(1-C), 63.2 and 64.3 (OCH₂CH₂O), 74.3 (CHOH), 114.3 (2-C),

115.5 (CH᎐CH ), 116.1 (CH(OH)CH᎐CH ), 136.0 (CH᎐CH ),

᎐

2

137.3 (CH(OH)CH᎐CH ); (10a): 19.9 (CH ), 23.03 (CH ), 27.8

᎐

2

(CH₂), 30.2 (CH₂), 36.2 (CH₂), 36.9 (CH₂), 46.2 (1-C), 63.3

and 64.1 (OCH₂CH₂O), 72.9 (CHOH), 114.4 (2-C), 115.7

(CH᎐CH ), 116.4 (CH(OH)CH CH᎐CH ), 135.7 (CH᎐CH ),

᎐

2

(1S*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)-

pent-4-en-1-ol 8a. The product was a colourless oil (24%),

R_f0.33. HRMS: M 252.1728. C₁₅H₂₄O₃requires 252.1725.

137.4 (CH(OH)CH CH᎐CH ); m/z (EI) 252 (M⁺, 1.3%), 211

᎐

2 2

(42), 182 (55), 139 (36), 121 (30), 113 (57), 99 (100), 86 (62), 79

(55), 67 (57), 55 (66).

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

1465

View Article Online

(1R*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycyclohexan-1-yl)but-3-

en-1-ol 10b

30.8 (CH₂), 32.6 (CH₂), 32.8 (CH₂), 33.9 (CH₂), 36.3 (CH₂),

36.6 (CH₂), 37.0 (CH₂), 39.9 (CH₂), 46.8 and 50.2 (2 × 1-C),

62.76, 62.77, 63.5 and 63.7 (2 × OCH₂CH₂O), 75.0 and 76.2

Only alcohol isomer 10b was isolated as the non-reacted part of

the epimeric alcohol substrate 10a and 10b (1 : 4) in an oxida-

tion reaction for the preparation of the ketone 19 (vide infra).

The product was a colourless oil (55%), R_f0.17. HRMS: M

252.1720. C₁₅H₂₄O₃requires 252.1725. ν_max(ﬁlm)/cm^Ϫ13500

(2 × CHOH), 115.6, 115.9, 116.03 and 116.7 (2 × CH᎐CH ,

᎐

2

2 × HC(OH)CH CH᎐CH ), 116.09 and 116.5 (2 × 1-C), 136.5,

᎐

2

136.8, 137.6 and 137.7 (2 × CH᎐CH , 2 × HC(OH)CH₂-

᎐

2

CH᎐CH ); m/z (EI) 266 (M⁺, 3%), 225 (100), 196 (75), 155 (29),

᎐

2

139 (45), 99 (93), 55 (23).

(O–H), 2935, 2860 (C–H), 1635 (C᎐C); δ (CDCl ) 1.21–1.71

᎐

H

3

(8 H, m, 4 × CH₂), 2.20–2.46 (4 H, m, 2 × CH₂), 3.66–3.90

(1 H, m, CHOH), 3.86–4.01 (5 H, m, 1 H from CHOH, 4 H

1-(1-Allyl-2,2-ethylenedioxycycloheptan-1-yl)pent-4-en-1-ol 14a

and 14b

from OCH CH O), 4.92–5.09 (4 H, m, 2 × CH᎐CH ), 5.81–5.97

᎐

2

(2 H, m, 2 × CH᎐CH ); δ (CDCl ) 20.2 (CH ), 23.1 (CH ), 30.1

(CH₂), 30.7 (CH₂), 33.5 (CH₂), 36.1 (CH₂), 46.6 (1-C), 63.3

and 64.4 (OCH₂CH₂O), 74.4 (CHOH), 114.4 (2-C), 115.6

᎐

2

C

3

2

The isomer mixture of 14a and 14b (1 : 1) was obtained follow-

ing the procedure described above from the carbaldehyde 5c

and 4-bromobut-1-ene. The product was a colourless oil (76%),

R_f0.31. HRMS: M. 280.2035. C₁₇H₂₈O₃requires 280.2038.

ν_max(ﬁlm)/cm^Ϫ13502 (O–H), 3045, 2910, 2847 (C–H), 1634

(CH᎐CH ), 116.2 (CH(OH)CH CH᎐CH ), 136.1 (CH᎐CH ),

᎐

2

137.5 (CH(OH)CH CH᎐CH ); m/z (EI) 252 (M⁺, 12%), 211

᎐

2

(10), 168 (36), 124 (22), 99 (100), 86 (25), 55 (29).

(C᎐C); δ (CDCl ) 1.44–1.75 (12 H, m, 6 × CH ), 1.98–2.39

᎐

H

3

2

(4 H, m, 2 × CH₂), 3.13–3.70 (2 H, d, J 6, CHOH (14a), dd,

J 10, 6, CHOH (14a), d, J 2, CHOH (14b), dd, J 4, 2, CHOH

(14b)), 3.85–3.97 (4 H, m, OCH₂CH₂O), 4.89–5.03 (4 H,

(1R*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycyclohexan-1-yl)pent-4-

en-1-ol 11b

2 × CH᎐CH ), 5.78–5.95 (2 H, m, 2 × CH᎐CH ); δ (CDCl )

᎐

2

C

3

Compound 11b was obtained following the procedure

described above from the carbaldehyde 5b and 4-bromobut-1-

ene as a colourless oil (75%), R_f0.41. HRMS: M 266.1880.

C₁₆H₂₆O₃requires 266.1881. ν_max(ﬁlm)/cm^Ϫ13500 (O–H), 3050,

21.6 (CH₂), 22.4 (CH₂), 22.7 (CH₂), 22.8 (CH₂), 28.4 (CH₂),

29.6 (CH₂), 29.8 (CH₂), 31.0 (CH₂), 31.3 (CH₂), 31.5 (2 × CH₂),

32.7 (CH₂), 33.0 (CH₂), 34.1 (CH₂), 36.4 (CH₂), 37.8 (CH₂),

49.9 and 50.4 (2 × 1-C), 62.7, 62.73, 63.6 and 63.7 (2 × OCH₂-

CH₂O), 75.1 and 75.9 (2 × CHOH), 114.2, 114.4, 115.9 and

2910, 2860 (C–H), 1603 (C᎐C); δ (CDCl ) 1.34–1.71 (10 H, m,

᎐

H

3

5 × CH ), 2.02–2.07 (1 H, m, CHCH᎐CH ), 2.29–2.36 (3 H, m,

᎐

2

116.7 (2 × CH᎐CH , 2 × HC(OH)(CH ) CH᎐CH ), 116.1 and

᎐

2

CHCH᎐CH , CH CH᎐CH ), 3.63–3.65 (1 H, m, CHOH), 3.88–

᎐

2

116.2 ( 2 × 2-C), 136.6, 136.9, 139.1 and 139.2 (2 × CH᎐CH2,

᎐

3.99 (5 H, m, 4 from OCH₂CH₂O, 1 from CHOH), 4.90–5.05

(4 H, m, 2 × CH᎐CH ), 5.76–5.98 (2 H, m, 2 × CH᎐CH );

2 × HC(OH)(CH ) CH᎐CH d); m/z (EI) 280 (M⁺, 7%), 239

᎐

2

᎐

2

(25), 196 (100), 153 (15), 99 (51), 55 (14).

δ_C(CDCl₃) 20.3 (CH₂), 23.2 (CH₂), 30.3 (CH₂), 30.7 (CH₂), 30.8

(CH₂), 31.4 (CH₂), 33.6 (CH₂), 46.7 (1-C), 63.3 and 64.5

1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)prop-2-en-1-one 15

and recovered alcohol 6b

(OCH CH O), 73.9 (CHOH), 114.4 (CH᎐CH ), 114.6 (2-C),

᎐

2

116.0 (HC(OH)(CH ) CH᎐CH ), 136.4 (CH᎐CH ), 139.1

᎐

2

(HC(OH)(CH ) CH᎐CH ); m/z (EI) 266 (M⁺, 13%), 225 (26),

᎐

2

The mixture of the alcohols 6a and 6b (8 : 1; 0.448 g, 2 mmol)

in dichloromethane (3 ml) was added rapidly at ambient

temperature to a suspension of pyridinium chlorochromate

(0.648 g, 3 mmol) in dichloromethane (4 ml). The mixture

became brieﬂy homogeneous before a black precipitate was

formed. TLC monitoring showed that the reaction had gone to

completion after 6 h. The reaction mixture was diluted with 5

volumes of anhydrous diethyl ether, the solvent decanted, the

black solid washed twice with diethyl ether and the combined

ethereal solution ﬁltered through Florisil. Evaporation of

ﬁltrate and ﬂash chromatography of the residual material

using hexane–EtOAc 10 : 1, R_f0.33, led to separation of the

ketone 15 and the alcohol 6b. The ketone was ﬁrst eluted and

was obtained as a colourless oil (0.328 g, 70%). HRMS: M

222.1247. C₁₃H₁₈O₃requires 222.1255. ν_max(ﬁlm)/cm^Ϫ13020,

182 (91), 163 (11), 139 (23), 127 (31), 99 (100), 86 (27), 67 (16),

55 (22).

(1S*,1ЈS*)-1-(1-Allyl-2,2-ethylenedioxycycloheptan-1-yl)prop-

2-en-1-ol 12a

Compound 12a was obtained following the procedure

described above from the carbaldehyde 5c and vinylmagnesium

chloride as a colourless oil (78%), R_f0.22. HRMS: M 252.1276.

C₁₅H₂₄O₃requires 252.1725. ν_max(ﬁlm)/cm^Ϫ13500 (O–H), 3038,

2960, 2875 (C–H), 1635 (C᎐C); δ (CDCl ) 1.47–1.72 (10 H, m,

᎐

H

3

5 × CH ), 2.26–2.29 (2 H, d, J 8, CH CH᎐CH ), 3.80–3.82 (1 H,

᎐

2

d, J 6, CHOH), 3.85–3.94 (4 H, m, OCH₂CH₂O), 4.20–4.24

(1H, m, CHOH), 4.93–5.25 (4H, m, 2 × CH᎐CH ), 5.85–6.06

᎐

2

(2 H, m, 2 × CH᎐CH ); δ (CDCl ) 21.8 (CH ), 22.5 (CH ),

᎐

2

C

3

2

2960, 2880 (C–H), 1680 (C᎐O),1600 (C᎐C); δ (CDCl ) 1.54–

᎐

28.6 (CH₂), 32.5 (CH₂), 33.2 (CH₂), 36.3 (CH₂), 50.1 (1-C), 62.7

and 63.6 (OCH CH O), 77.4 (CHOH), 114.8 (CH᎐CH ), 116.4

H

3

1.82 (5 H, m, 2 × CH₂, 1 H from CH₂), 2.17–2.24 (1 H, dd,

J 14.5, 8, CH CH᎐CH ), 2.30–2.40 (1 H, m, CH ), 2.74–2.82

᎐

2

᎐

(2-C), 116.6 (HC(OH)CH᎐CH ), 136.8 (CH᎐CH ), 138.1

2

᎐

2

(HC(OH)CH᎐CH ); m/z (EI) 256 (M⁺, 1%), 211 (15), 197 (11),

2

(1 H, dd, J 14.5, 6.5, CH CH᎐CH ), 3.75–3.92 (4 H, m, OCH -

᎐

2

CH O), 4.93–5.01 (2 H, m, CH CH᎐CH ), 5.38–5.48 (1 H, m,

᎐

168 (43), 139 (45), 99 (100), 55 (37).

2

CH CH᎐CH ), 5.49–5.51 (1 H, dd, J 10, 2, COCH᎐CH ), 6.17–

᎐

2

6.23 (1 H, dd, J 17, 2, COCH᎐CH ), 6.74–6.83 (1 H, dd, J 17,

᎐

1-(1-Allyl-2,2-ethylenedioxycycloheptan-1-yl)but-3-en-1-ol 13a

and 13b

2

10, COCH᎐CH ); δ (CDCl ) 18.5 (CH ), 28.6 (CH ), 34.9

᎐

2

C

3

2

(CH₂), 36.8 (CH₂), 61.1 (1-C), 64.1 and 64.8 (OCH₂CH₂O),

118.0 (CH᎐CH ), 118.6 (2-C), 126.4 (COCH᎐CH ), 133.1

The isomer mixture of 13a and 13b (1 : 1) was obtained follow-

ing the procedure described above from the carbaldehyde 5c

and allyl bromide. The product was a colourless oil (83%),

R_f0.32. HRMS: M 266.1881. C₁₆H₂₆O₃requires 266.1882.

ν_max(ﬁlm)/cm^Ϫ13505 (O–H), 3070, 2910, 2895 (C–H), 1640

᎐

2

(CH᎐CH ), 133.5 (COCH᎐CH ), 199.7 (C᎐O); m/z (EI) 222

᎐

2

(M⁺, 2%), 167 (5), 139 (7), 112 (8), 99 (100), 79 (4), 67 (6), 55

(24).

The second product was the epimer pure alcohol 6b that was

obtained as an oil in 4% yield. The physical data are given above.

(C᎐C); δ (CDCl ) 1.39–1.62 (10 H, m, 5 × CH ), 2.08–2.42

᎐

H

3

2

(4 H, m, 2 × CH₂), 3.12–3.82 (2 H, d, J 5, CHOH (13a), d, J 4,

CHOH (13b), dd, J 10, 4, CHOH (13a), dd, J 10, 5, CHOH

(13b)), 3.83–3.99 (4H, m, OCH₂CH₂O), 4.92–5.07 (4 H, m,

1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)but-3-en-1-one 16

and recovered alcohol 7b

CH CH᎐CH , CH(OH)CH CH᎐CH ), 5.83–6.02 (2 H, m,

᎐

2

CH CH᎐CH , CH(OH)CH CH᎐CH ); δ (CDCl ) 21.6 (CH ),

The oxidation was carried out following the procedure

᎐

2

C

3

2

22.4 (CH₂), 22.73 (CH₂), 22.76 (CH₂), 28.3 (CH₂), 29.6 (CH₂),

described above with a mixture of the alcohols 7a and 7b (1 : 4)

1466 J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

View Article Online

and pyridinium chlorochromate in dichloromethane for 3 h.

The products were separated by ﬂash chromatography. The

ketone was ﬁrst eluted and was obtained as a colourless oil

(47%), R_f0.36. HRMS: M 236.1420. C₁₄H₂₀O₃requires

(1 H, dd, J 15, 7, CH CH᎐CH ), 3.21–3.44 (2 H, m, COCH -

᎐

2 2 2

CH᎐CH ), 3.79–3.94 (4 H, m, OCH CH O), 4.90–5.05 (4 H, m,

᎐

2

2 × ᎐CH ), 5.32–5.53 (1 H, m, CH CH᎐CH ), 5.78–5.99 (1 H,

᎐

2

m, COCH CH᎐CH ); δ (CDCl ) 20.5 (CH ), 22.9 (CH ), 28.9

᎐

2

C

3

2

236.1412. ν_max(ﬁlm)/cm^Ϫ13060, 2975, 2890 (C–H), 1700 (C᎐O),

(CH₂), 31.7 (CH₂), 35.1 (CH₂), 45.2 (CH₂), 58.6 (1-C), 63.9

and 64.4 (OCH CH O), 110.8 (2-C), 117.1 (CH᎐CH ), 117.9

᎐

1645 (C᎐C); δ (CDCl ) 1.57–1.79 (5 H, m, 2 × CH , 1 H from

᎐

H

3

2

CH ), 2.13–2.20 (1 H, dd, J 14.5, 7, CH CH᎐CH ), 2.28–2.48

(COCH CH᎐CH ), 132.2 (CH᎐CH ), 133.2 (COCH CH᎐CH ),

᎐ ᎐ ᎐

2 2 2 2 2

᎐

2

(1 H, m, CH ), 2.76–2.83 (1 H, dd, J 14.5, 7, CH CH᎐CH ),

209.9 (C᎐O); m/z (EI) 264 (M⁺, 12%), 223 (6), 181 (82), 139

᎐

2

3.20–3.25 (2 H, m, COCH CH᎐CH ), 3.76–3.99 (4 H, m,

(169), 112 (17), 99 (100), 86 (50), 55 (75).

The second product was the pure alcohol isomer 10b that

was a colourless oil in 55% yield. The physical data are given

above.

᎐

2

OCH CH O), 4.96–5.09 (4 H, m, 2 × ᎐CH ), 5.41–5.55 (1 H,

᎐

2

m, CH CH᎐CH ), 5.82–5.95 (1 H, m, COCH CH᎐CH );

᎐

2

δ_C(CDCl₃) 18.8 (CH₂), 29.0 (CH₂), 34.8 (CH₂), 37.1 (CH₂),

44.4 (CH₂), 62.1 (1-C), 63.9 and 64.7 (OCH₂CH₂O), 117.4

(CH᎐CH ), 118.1 (COCH CH᎐CH ), 118.6 (2-C), 131.9

᎐

2

1-(1-Allyl-2,2-ethylenedioxycyclohexan-1-yl)pent-4-en-1-one 20

(CH᎐CH ), 133.6 (COCH CH᎐CH ), 208.9 (C᎐O); m/z (EI) 236

᎐

2

(M⁺, 5%), 195 (35), 167 (30), 99 (100), 55 (6).

Compound 20 was obtained following the procedure described

above by oxidation of the alcohol 11b using pyridinium chloro-

chromate in dichloromethane for 10 h. The ketone was a

colourless oil (78%), R_f0.27. HRMS: M 264.1722. C₁₆H₂₄O₃

requires 264.1725. ν_max(ﬁlm)/cm^Ϫ12910, 2840 (C–H), 1680

The second product was the pure alcohol isomer 7b that was

obtained as an oil in 33% yield. The physical data are given

above.

(C᎐O), 1625 (C᎐C); δ (CDCl ) 1.46–1.63 (7 H, m, 3 × CH , 1 H

᎐

H

3

2

1-(1-Allyl-2,2-ethylenedioxycyclopentan-1-yl)pent-4-en-1-one 17

from CH₂), 2.01–2.16 (2 H, m, CH₂), 2.18–2.28 (1 H, m, CH₂),

2.20–2.39 (1 H, dd, J 14, 8, CH CH᎐CH ), 2.60–2.70 (2 H, m,

Compound 17 was obtained from the alcohol 8a by oxidation

with pyridinium chlorochromate in CH₂Cl₂for 9 h following

the procedure described above as a colourless oil (81%), R_f0.34.

HRMS: M 250.1567. C₁₅H₂₂O₃requires 250.1568. ν_max(ﬁlm)/

cm^Ϫ13070, 2981, 2890 (C–H), 1698 (C᎐O), 1643 (C᎐C);

᎐

2

CH ), 2.72–2.80 (1 H, dd, J 14, 8, CH CH᎐CH ), 3.85–3.94

᎐

2

(4 H, m, OCH CH O), 4.93–5.03 (4 H, m, 2 × CH ᎐), 5.41–5.53

᎐

2

(1 H, m, CH CH᎐CH ), 5.72–5.85 (1 H, m, CO(CH ) -

᎐

2

2 2

CH᎐CH ); δ (CDCl ) 20.6 (CH ), 23.0 (CH ), 27.9 (CH ), 29.2

᎐

2

C

3

2

δ_H(CDCl₃) 1.57–1.76 (5 H, m, 1 H from CH₂, 2 × CH₂), 2.10–

2.39 (4 H, m, 2 × CH₂), 2.49–2.56 (2 H, m, 1 H from CH₂, 1 H

(CH₂), 31.8 (CH₂), 35.5 (CH₂), 40.0 (CH₂), 58.5 (1-C), 64.0 and

64.4 (OCH CH O), 111.1 (2-C), 114.7 (CH᎐CH ), 127.8 (CO-

᎐

2

from CH CH᎐CH ), 2.75–2-86 (1 H, dd, J 14.5, 7, CH -

(CH ) CH᎐CH ), 133.5 (CH᎐CH ), 138.1 (CO(CH₂)₂-

᎐ ᎐

2 2 2 2

᎐

2

CH᎐CH ), 3.79–3.93 (4 H, m, OCH CH O), 4.87–5.07 (4 H, m,

CH᎐CH ), 211.2 (C᎐O); m/z (EI) 264 (M⁺, 18%), 223 (6), 181

᎐ ᎐

2

᎐

2

2 × CH ᎐), 5.38–5.59 (1 H, m, CH CH᎐CH ), 5.67–5.88 (1 H,

(82), 112 (17), 99 (100), 86 (49), 55 (75).

᎐

2

m, CO(CH ) CH᎐CH ); δ (CDCl ) 18.8 (CH ), 27.8 (CH ),

᎐

2

C

3

2

29.2 (CH₂), 34.9 (CH₂), 37.3 (CH₂), 39.2 (CH₂), 62.0 (1-C), 63.9

and 64.7 (OCH CH O), 114.6 (CH᎐CH ), 117.9 (CO(CH ) -

1-(1-Allyl-2,2-ethylenedioxycycloheptan-1-yl)prop-2-en-1-one 21

᎐

2

2 2

Compound 21 was obtained following the procedure described

above by oxidation of the alcohol 12a using pyridinium chloro-

chromate in dichloromethane for 5 h The ketone was a colour-

less oil (82%), R_f0.31. HRMS: M 250.1566. C₁₅H₂₂O₃requires

CH᎐CH ), 118.7 (2-C), 133.8 (CH᎐CH ), 138.0 (CO(CH ) -

᎐

2

2 2

CH᎐CH ), 210.2 (C᎐O); m/z (EI) 250 (M⁺, 0.4%), 167 (16), 139

᎐

2

(6), 123 (5), 112 (11), 99 (100), 67 (12), 55 (46).

250.1568. ν_max(ﬁlm)/cm^Ϫ12910, 2840 (C–H), 1685 (C᎐O), 1630

᎐

1-(1-Allyl-2,2-ethylenedioxycyclohexan-1-yl)prop-2-en-1-one 18

(C᎐C); δ (CDCl ) 1.21–1.79 (9 H, m, 4 × CH , 1 H from CH ),

᎐

H

3

2

Compound 18 was obtained following the procedure described

above from the oxidation of the alcohol 9a using pyridinium

chlorochromate in dichloromethane for 6 h. The ketone was

obtained as a colourless oil (70%), R_f0.38. HRMS: M

236.1416. C₁₄H₂₀O₃requires 236.1412. ν_max(ﬁlm)/cm^Ϫ12950,

2.16–2.24 (1 H, m, CH₂), 2.26–2.33 (1 H, dd, J 14, 8,

CH CH᎐CH ), 2.80–2.88 (1 H, dd, J 14, 7, CH CH᎐CH ),

᎐

2

3.79–3.92 (4 H, m, OCH CH O), 4.91–5.00 (2 H, m, 2 × CH ᎐),

᎐

2

5.44–5.50 (1 H, dd, J 10, 2, COCH᎐CH ), 5.52–5.55 (1 H,

᎐

2

m, CH CH᎐CH ), 6.14–6.20 (1 H, dd, J 17, 2, COCH᎐CH ),

᎐

2

2880 (C–H), 1680 (C᎐O), 1600 (C᎐C); δ (CDCl ) 1.20–1.67

6.89–6.98 (1 H, dd, J 17, 10, COCH᎐CH ); δ (CDCl ) 22.1

᎐

2 C 3

᎐

H

3

(7 H, m, 1 H from CH₂, 6 H from 3 × CH₂), 2.01–2.06 (1 H, m,

CH ), 2-38–2.46 (1 H, dd, J 15, 8, CH CH᎐CH ), 2.78–2.85

(CH₂), 22.9 (CH₂), 28.8 (CH₂), 31.2 (CH₂), 33.9 (CH₂), 38.0

(CH₂), 60.1 (1-C), 63.1 and 64.2 (OCH₂CH₂O), 113.5 (2-C),

᎐

2

(1 H, dd, J 15, 6, CH CH᎐CH ), 3.78–3.91 (4 H, m, OCH -

117.8 (CH᎐CH ), 125.9 (COCH᎐CH ), 133.6 (CH᎐CH ), 134.0

᎐ ᎐ ᎐

2 2 2

᎐

2

CH O), 4.93–5.01 (2 H, m, CH᎐CH ), 5.36–5.42 (1 H, m,

(COCH᎐CH ), 200.3 (C᎐O); m/z (EI) 252 (M⁺, 3%), 209 (25),

᎐ ᎐

2

᎐

2

CH CH᎐CH ), 5.44–5.50 (1 H, dd, J 10, 2, COCH᎐CH ),

195 (68), 139 (23), 99 (100), 55 (26).

᎐

2

6.15–6.21 (1 H, dd, J 17, 2, COCH᎐CH ), 7.00–7.09 (1 H, dd,

᎐

2

J 17, 10, COCH᎐CH ); δ (CDCl ) 20.4 (CH ), 23.0 (CH ),

᎐

2

C

3

2

1-(1-Allyl-2,2-ethylenedioxycycloheptan-1-yl)but-3-en-1-one 22

28.5 (CH₂), 32.0 (CH₂), 34.6 (CH₂), 57.5 (1-C), 64.1 and

64.6 (OCH CH O), 111.3 (2-C), 118.0 (COCH᎐CH ), 123.3

The oxidation was carried out following the procedure described

above with a mixture of the alcohols 13a and 13b (1 : 1) and

᎐

2

(CH᎐CH ), 132.9 (CH᎐CH ), 134.2 (COCH᎐CH ), 200.9

᎐

2

(C᎐O); m/z (EI) 236 (M⁺, 24%), 208 (10), 195 (46), 181 (92),

pyridinium chlorochromate in dichloromethane for

7 h.

᎐

The ketone was obtained as a colourless oil (88%) after ﬂash

chromatography, R_f0.29. HRMS: M 264.1733. C₁₆H₂₄O₃

requires 264.1725. ν_max(ﬁlm)/cm^Ϫ12915, 2856 (C–H), 1690

139 (26), 125 (28), 112 (32), 99 (100), 86 (61), 55 (44).

1-(1-Allyl-2,2-ethylenedioxycyclohexan-1-yl)but-3-en-1-one 19

and recovered alcohol 10b

(C᎐O), 1636 (C᎐C); δ (CDCl ) 1.43–1.80 (9 H, m, 4 × CH , 1 H

᎐

H

3

2

from CH₂), 2.14–2.23 (1 H, m, from CH₂), 2.24–2.31 (1 H, dd,

J 15, 8, CH CH᎐CH ), 2.80–2.88 (1 H, m, CH CH᎐CH ),

The oxidation was carried out following the procedure

described above with a mixture of the alcohols 10a and 10b

(1 : 4) and pyridinium chlorochromate in dichloromethane for

4 h. The products were separated by ﬂash chromatography. The

ketone was a colourless oil (40%), R_f0.24. HRMS: 250.1567.

C₁₅H₂₂O₃requires 250.1568. ν_max(ﬁlm)/cm^Ϫ12920, 2865 (C–H),

᎐

2

3.21–3.41 (2 H, m, COCH CH᎐CH ), 3.82–3.94 (4 H, m,

᎐

2

OCH CH O), 4.95–5.07 (4 H, m, 2 × ᎐CH ), 5.44–5.58 (1 H,

᎐

2

m, CH CH᎐CH ), 5.85–5.98 (1 H, m, COCH CH᎐CH );

᎐

2

δ_H(CDCl₃) 22.1 (CH₂), 23.0 (CH₂), 29.1 (CH₂), 31.7 (CH₂), 33.5

(CH₂), 38.4 (CH₂), 44.5 (CH₂), 61.4 (1-C), 62.9 and 64.0

1690 (C᎐O), 1630 (C᎐C); δ (CDCl ) 1.40–2.10 (8 H, m,

(OCH CH O), 113.4 (2-C), 117.0 (CH᎐CH ), 117.9 (COCH -

᎐

2 2 2 2

᎐

H

3

4 × CH ), 2.26–2.37 (1 H, dd, J 15, 8, CH CH᎐CH ), 2.72–2.82

CH᎐CH ), 132.7 (CH᎐CH ), 133.9 (COCH CH᎐CH ), 209.4

᎐ ᎐ ᎐

2 2 2 2

᎐

2

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

1467

View Article Online

(C᎐O); m/z (EI) 264 (M⁺, 3%), 223 (100), 195 (57), 153 (7), 139

trans- and cis-1,1-Ethylenedioxyspiro[4.5]dec-8-en-6-ol 25a and

᎐

(11), 99 (63), 67 (12), 55 (6).

25b

The RCM reaction was carried out following the procedure

described above with a mixture of the alcohols 7a and 7b (1 : 4)

and 5 mol% Ru()-catalyst at 30 ЊC for 0.5 h. The epimeric

alcohols were separated by ﬂash chromatography using

CH₂Cl₂–EtOAc 8 : 1. Compound 25b was eluted ﬁrst.

1-(1-Allyl-2,2-ethylenedioxycycloheptan-1-yl)pent-4-en-1-one 23

The oxidation was carried out following the procedure

described above with a mixture of the alcohols 14a and 14b

(1 : 1) and pyridinium chlorochromate in dichloromethane for

7 h. The ketone was obtained as a colourless oil (85%) after

ﬂash chromatography, R_f0.42. HRMS: M 278.1878. C₁₇H₂₆O₃

requires 278.1882. ν_max(ﬁlm)/cm^Ϫ12915, 2856 (C–H), 1700

cis-1,1-Ethylenedioxyspiro[4.5]dec-8-en-6-ol 25b. A colourless

oil (74%), R_f0.54 (Found: C, 68.40; H, 8.87. C₁₂H₁₈O₃requires

C, 68.57; H, 8.57%). HRMS: M 210.1259. C₁₂H₁₈O₃requires

210.1255. ν_max(ﬁlm)/cm^Ϫ13480, (C–OH), 3004, 2900, 2890

(C᎐O), 1639 (C᎐C); δ (CDCl ) 1.29–1.80 (9 H, m, 1 H from

᎐

H

3

CH₂, 4 × CH₂), 2.15–2.67 (6 H, m, 1 H from CH₂, 1 H from

CH CH᎐CH , 2 × CH ), 2.81–2.88 (1H, dd, J 14, 7, CH -

᎐

2

(C–H), 1650 (C᎐C); δ (CDCl ) 1.46–2.00 (8 H, m, 4 × CH ),

᎐

H

3

2

CH᎐CH ), 3.82–3.88 (4 H, m, OCH CH O), 4.88–5.04 (4 H, m,

᎐

2

2.16–2.34 (2 H, m, CH₂), 3.87–3.96 (6 H, m, 1 H from CHOH,

1 H from CHOH, 4 H from OCH₂CH₂O), 5.45–5.62 (2 H, m,

2 × CH᎐CH ), 5.44–5.58 (1 H, m, CH CH᎐CH ), 5.69–5.85

᎐

2

(1 H, m, CO(CH ) CH᎐CH ); δ (CDCl ) 22.1 (CH ), 23.1

᎐

2

C

3

2

2 × CH᎐); δ (CDCl ) 19.1 (CH ), 26.8 (CH ), 31.8 (CH ), 33.2

᎐

C

3

2

(CH₂), 28.3 (CH₂), 29.2 (CH₂), 32.0 (CH₂), 33.5 (CH₂), 38.7

(CH₂), 39.2 (CH₂), 61.1 (1-C), 62.3 and 64.0 (OCH₂CH₂O),

(CH₂), 36.1 (CH₂), 49.1 (6-C), 64.0 and 64.4 (OCH₂CH₂O), 68.8

(CHOH), 120.5 (7-C), 124.6 (4-CH᎐), 124.9 (3-CH᎐); m/z (EI)

᎐

210 (M⁺, 3%), 191 (26), 167 (10), 148 (30), 130 (26), 104 (34),

99 (100), 86 (22), 55 (13).

113.4 (2-C), 114.5 (CH᎐CH ), 117.7 (CO(CH ) CH᎐CH ),

᎐

2

134.1 (CH᎐CH ), 138.2 (CO(CH ) CH᎐CH ), 210.8 (C᎐O);

᎐

2

m/z (EI) 278 (M⁺, 13%), 237 (25), 195 (98), 139 (17), 127 (59), 99

(100), 55 (15).

trans-1,1-Ethylenedioxyspiro[4.5]dec-8-en-6-ol 25a. A colour-

less oil (16%), R_f0.42 (Found: C, 68.80; H, 8.59. C₁₂H₁₈O₃

requires C, 68.57; H, 8.57%). HRMS: M 210.1249. C₁₂H₁₈O₃

requires 210.1255. ν_max(ﬁlm)/cm^Ϫ13496, (C–OH), 3010, 2910,

trans- and cis-6,6-Ethylenedioxyspiro[4.4]non-2-en-1-ol 24a and

24b

2870 (C–H), 1640 (C᎐C); δ (CDCl ) 1.46–1.62 (4 H, m,

Bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride

(20.5 mg, 0.025 mmol) in dry toluene (1 ml), was added to

a solution of the epimeric alcohols 6a and 6b (8 : 1) (0.224 g,

1 mmol) in dry toluene (20 ml) under argon. The mixture was

stirred and heated under argon at 70 ЊC for 2 h when another

portion of bis(tricyclohexylphosphine)(benzylidene)ruthenium

dichloride (20.5 mg, 0.025 mmol) in dry toluene (1 ml) was

added. The heating was continued at 70 ЊC for 4 h. The cold

reaction mixture was ﬁltered, the ﬁltrate evaporated and the

residual material subjected to ﬂash chromatography using

CH₂Cl₂–EtOAc 8 : 1, R_f0.21. The yield of the alcohols 24a and

24b (8 : 1) was 0.156 g (80%) as a colourless oil (Found: C,

67.60; H, 8.37. C₁₁H₁₆O₃requires C, 67.34; H, 8.16%). HRMS:

M 196.1098. C₁₁H₁₆O₃requires 196.1099. ν_max(ﬁlm)/cm^Ϫ13505,

᎐

H

3

2 × CH₂), 1.73–1.80 (3 H, m, CH₂, 1 H from CH₂), 2.05–2.18

(2 H, m, CH₂), 2.34–2.42 (1 H, m, from CH₂), 3.39 (1 H, s,

CHOH), 3.83–3.98 (4 H, m, OCH₂CH₂O), 4.01 (1 H, s,

CHOH), 5.50–5.54 (1 H, m, CH᎐), 5.60–5.65 (1 H, m, CH᎐);

᎐

δ_C(CDCl₃) 17.8 (CH₂), 27.0 (CH₂), 30.8 (CH₂), 32.0 (CH₂), 32.8

(CH₂), 47.0 (6-C), 64.1 and 64.4 (OCH₂CH₂O), 68.2 (CHOH),

119.5 (7-C), 123.0 (4-CH᎐), 125.0 (3-CH᎐); (EI) 210 (M⁺, 2%),

᎐

191 (25), 148 (35), 104 (33), 99 (100), 86 (22), 55 (16).

trans-1,1-Ethylenedioxyspiro[4.6]undec-9-en-6-ol 26a

The RCM reaction was carried out following the procedure

described above with the alcohol epimer 8a and 5 mol%

Ru()-catalyst at 60 ЊC for 4 h. The product after ﬂash

chromatography was a colourless oil (75%), R_f0.48 (Found:

C, 69.39; H, 9.1. C₁₃H₂₀O₃requires C, 69.64; H, 8.92%).

HRMS: M 224.1405. C₁₃H₂₀O₃requires 224.1412. ν_max(ﬁlm)/

3480 (C–OH), 3010, 2945, 2870 (C–H), 1610 (C᎐C); δ (CDCl )

᎐

H

3

1.62–2.14 (7 H, m, 3 × CH₂, 1 H from CH₂), 2.51–2.75 (1H, dq,

J 17, 5, 2, 1 H from CH₂), 3.19–3.80 (1 H, 3.20, d, J 7, CHOH-

(trans), 3.80–3.85 (1 H, m, CHOH (cis)), 3.85–3.98 (4 H, m,

OCH₂CH₂O), 4.37–4.74 (1 H, 4.39, dt, J 7, 2, CHOH(trans)),

cm^Ϫ13501, (C–OH), 3000, 2930, 2878 (C–H), 1645 (C᎐C);

᎐

δ_H(CDCl₃) 1.48–2.18 (12 H, m, 6 × CH₂), 3.75 (1 H, dd, J 9,

4, CHOH), 3.80–3.96 (4 H, m, OCH₂CH₂O), 4.23 (1 H, s,

4.73 (1 H, d, J 5, CHOH(cis)), 5.67–5.76 (1 H, m, CH᎐), 5.86–

᎐

5.90 (1 H, m, CH᎐); δ (CDCl ) (trans): 18.0 (CH ), 33.4 (CH ),

᎐

C

3

2

CHOH), 5.49–5.57 (1 H, m, CH᎐), 5.75–5.83 (1 H, m, CH᎐);

᎐

37.0 (CH₂), 38.6 (CH₂), 54.9 (5-C), 63.4 and 65.1 (OCH₂CH₂O),

83.1 (CHOH), 118.8 (6-C), 132.7 (3-CH᎐), 133.6 (2-CH᎐);

δ_C(CDCl₃) 18.7 (CH₂), 23.5 (CH₂), 25.4 (CH₂), 30.3 (CH₂), 31.5

(CH₂), 34.1 (CH₂), 52.0 (7-C), 63.5 and 64.7 (OCH₂CH₂O), 74.6

᎐

(cis): 17.9 (CH₂), 29.5 (CH₂), 33.4 (CH₂), 40.1 (CH₂), 57.9 (5-C),

64.3 and 64.9 (OCH₂CH₂O), 78.2 (CHOH), 118.9 (6-C), 131.2

(3-CH᎐), 132.6 (2-CH᎐); m/z (EI) 196 (M⁺, 8%), 178 (11), 153

(CHOH), 121.8 (8-C), 127.5 (5-CH᎐), 133.1 (4-CH᎐); m/z (EI)

᎐

224 (M⁺, 8%), 206 (7), 180 (9), 162 (15), 120 (24), 99 (100),

86 (27), 55 (20).

᎐

(12), 134 (17), 106 (14), 99 (100), 92 (64), 79 (15), 55 (30).

cis-6,6-Ethylenedioxyspiro[4.4]non-2-en-1-ol 24b

cis-1,1-Ethylenedioxyspiro[4.6]undec-9-en-6-ol 26b

When the RCM reaction was repeated following the procedure

described above with epimerically pure alcohol 6b the corre-

sponding cis product 24b was obtained as a colourless oil

(79%), R_f0.21. HRMS: M 196.1097. C₁₁H₁₆O₃requires

196.1099. ν_max(ﬁlm)/cm^Ϫ13489, (C–OH), 3020, 2940, 2880 (C–

When the RCM reaction was repeated following the procedure

described above with epimerically pure alcohol 8b the corre-

sponding cis product 26b was obtained as a colourless oil

(90%), R_f0.42 (Found: C, 69.81; H, 9.21. C₁₃H₂₀O₃requires C,

69.64; H, 8.92%). HRMS: M 224.1412. C₁₃H₂₀O₃requires

224.1412. ν_max(ﬁlm)/cm^Ϫ13485, (C–OH), 3000, 2910, 2860

H), 1624 (C᎐C); δ (CDCl ) 1.67–1.96 (6 H, m, 3 × CH ), 1.98–

᎐

H

3

2

2.05 (1 H, dt, J 17, 2, from CH₂), 2.69–2.77 (1 H, dq, J 17, 4,

2, from CH₂), 3.77–3.80 (1 H, m, CHOH), 3.87–4.00 (4 H, m,

OCH₂CH₂O), 4.74 (1 H, d, J 5, CHOH), 5.75–5.78 (1 H, m,

(C–H), 1640 (C᎐C); δ (CDCl ) 1.41–1.92 (10 H, m, 5 × CH ),

᎐

H 3 2

2.51–2.81 (2 H, m, CH₂), 3.19 (1 H, t, J 2 CHOH), 3.79–3.99

(4 H, m, OCH₂CH₂O), 4.17 (1 H, t, J 2, CHOH), 5.53–5.66

CH᎐), 5.88–5.92 (1H, m, CH᎐); δ (CDCl ) 17.8 (CH ), 29.6

(1 H, m, CH᎐), 5.77–5.89 (1 H, m, CH᎐); δ (CDCl ) 17.6 (CH ),

᎐ ᎐

C 3 2

᎐

C

3

2

(CH₂), 33.4 (CH₂), 40.1 (CH₂), 57.8 (5-C), 64.4 and 64.9

20.6 (CH₂), 25.5 (CH₂), 29.0 (CH₂), 30.7 (CH₂), 32.8 (CH₂),

49.8 (7-C), 63.8 and 64.1 (OCH₂CH₂O), 72.7 (CHOH), 120.2

(8-C), 128.5 (5-CH᎐), 133.5 (4-CH᎐); m/z (EI) 224 (M⁺, 4%),

(OCH CH O), 78.2 (CHOH), 118.9 (6-C), 131.2 (3-CH᎐), 132.6

᎐

2

(2-CH᎐); m/z (EI) 196 (M⁺, 2%), 178 (6), 152 (44), 134 (35), 106

᎐

(35), 92 (100), 79 (68), 55 (30).

206 (5), 180 (10), 162 (11), 120 (22), 99 (100), 86 (24), 55 (17).

1468

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

View Article Online

trans-6,6-Ethylenedioxyspiro[4.5]dec-2-en-1-ol 27a

5.76–5.83 (1 H, m, CH᎐); δ (CDCl ) 20.0 (CH ), 20.5 (CH ),

᎐

C 3 2 2

23.3 (CH₂), 25.2 (CH₂), 26.8 (CH₂), 29.6 (CH₂), 30.0 (CH₂),

44.4 (7-C), 63.5 and 64.7 (OCH₂CH₂O), 72.5 (CHOH), 114.5

(8-C), 127.5 (5-CH᎐), 133.2 (4-CH᎐); m/z (EI) 238 (M⁺, 5%),

Compound 27a was obtained following the procedure

described above from the alcohol epimer 9a and 5 mol% of the

Ru()-catalyst at 60 ЊC for 4 h. The product was a colourless oil

(68%), R_f0.53 (Found: C, 68.35; H, 8.77. C₁₂H₁₈O₃requires C,

68.57; H, 8.57%). HRMS: M 210.1262. C₁₂H₁₈O₃requires

210.1256. ν_max(ﬁlm)/cm^Ϫ13505 (C–OH), 2910, 2815 (C–H),

᎐

176 (17), 148 (7), 134 (23), 125 (34), 112 (15), 99 (100), 91 (20),

86 (30), 79 (22), 67 (20), 55 (28).

trans-6,6-Ethylenedioxyspiro[4.6]undec-2-en-1-ol 30a

1590 (C᎐C); δ (CDCl ) 1.45–1.61 (7 H, m, 1 H from CH , 6 H

᎐

H

3

2

from 3 × CH₂), 1.73–1.83 (2 H, m, CH₂), 2.60–2.69 (1 H, dq,

J 17, 5, 2, 1 H from CH₂), 3.10 (1 H, d, J 10, CHOH ), 3.82–4.03

(4 H, m, OCH₂CH₂O), 4.37–4.42 (1 H, dt, J 10, 2, CHOH),

Compound 30a was obtained from the alcohol epimer 12a

using 5 mol% of Ru()-catalyst at 70 ЊC for 2 h. The product

was a colourless oil (71%), R_f0.51 (Found: C, 69.55; H, 8.77.

C₁₃H₂₀O₃requires C, 69.64; H, 8.92%). HRMS: M 224.1408.

C₁₃H₂₀O₃requires 224.1412. ν_max(ﬁlm)/cm^Ϫ13506 (C–OH),

5.67–5.70 (1 H, m, CH᎐), 5.76–5.80 (1 H, m, CH᎐); δ (CDCl )

᎐

C

3

21.4 (CH₂), 23.4 (CH₂), 31.6 (CH₂), 36.3 (CH₂), 40.5 (CH₂),

51.3 (5-C), 63.1 and 65.2 (OCH₂CH₂O), 80.9 (CHOH), 112.4

(s), 132.5 (3-CH᎐), 132.6 (2-CH᎐); m/z (EI) 210 (M⁺, 18%), 193

3010, 2935, 2880 (C–H), 1625 (C᎐C); δ (CDCl ) 1.44–1.81 (10

᎐

H

3

᎐

H, m, 5 × CH₂), 2.10–2.20 (1 H, m, CH₂), 2.63–2.71 (1 H, dq,

J 17, 4, 2, from CH₂), 3.09 (1H, d, J 10, CHOH), 3.83–4.00

(4 H, m, OCH₂CH₂O), 4.36–4.43 (1 H, dt, J 10, 2, CHOH),

(7), 153 (19), 148 (59), 137 (19), 122 (30), 99 (100), 95 (29), 86

(26), 55 (36).

5.68–5.72 (1 H, m, CH᎐), 5.78–5.82 (1 H, m, CH᎐); δ (CDCl )

᎐

C

3

trans- and cis-7,7-Ethylenedioxyspiro[5.5]undec-3-en-1-ol 28a

and 28b

19.8 (CH₂), 21.9 (CH₂), 26.1 (CH₂), 33.5 (CH₂), 36.9 (CH₂),

45.0 (CH₂), 54.8 (5-C), 63.5 and 64.7 (OCH₂CH₂O), 80.4

(CHOH), 114.3 (6-C), 132.4 (3-CH᎐), 132.9 (2-CH᎐); m/z (EI)

The RCM reaction was carried out following the procedure

described above with a mixture of the alcohols 10a and 10b

(1 : 4) and 5 mol% Ru()-catalyst at 28 ЊC for 0.5 h. The isomer

ratio of 28a and 28b was 1 : 4 after ﬂash chromatography. The

product was a colourless oil (94%), R_f0.32 (Found: C, 69.95;

H, 8.67. C₁₃H₂₀O₃requires C, 69.64; H, 8.92%). HRMS: M

224.1403. C₁₃H₂₀O₃requires 224.1412. ν_max(ﬁlm)/cm^Ϫ13480

᎐

224 (M⁺, 15%), 206 (17), 162 (26), 120 (31), 99 (100), 86 (25),

55 (11).

trans- and cis-7,7-Ethylenedioxyspiro[5.6]dodec-3-en-1-ol 31a

and 31b

The RCM reaction was carried out following the procedure

described above with a mixture of the alcohols 13a and 13b

(1 : 1) and 5 mol% Ru()-catalyst at 60 ЊC for 2 h. The product

after ﬂash chromatography was a mixture of the alcohol

epimers 31a and 31b in the ratio 1 : 1. The product was a

colourless oil (93%), R_f0.45. HRMS: M 238.1564. C₁₄H₂₂O₃

requires 238.1568. ν_max(ﬁlm)/cm^Ϫ13480 (C–OH), 3001, 2920,

(C–OH), 2920, 2860 (C–H), 1610 (C᎐C); δ (CDCl ) 1.30–2.34

(12 H, m, 6 × CH₂), 3.89–3.98 (4 H, m, OCH₂CH₂O), 4.00–4.20

(2 H, 4.01, s, CHOH(trans), 4.04, d, J 3, CHOH(cis), 4.13, s,

᎐

H

3

CHOH(trans), 4.20, s, CHOH(cis)), 5.42–5.49 (1 H, m, CH᎐),

᎐

5.57–5.62 (1 H, m, CH᎐); δ (CDCl ) (trans): 19.5 (CH ), 22.4

᎐

C

3

2

(CH₂), 22.9 (CH₂), 29.5 (CH₂), 29.7 (CH₂), 30.8 (CH₂), 45.5

(7-C), 63.4 and 64.3 (OCH₂CH₂O), 68.5 (CHOH), 114.8 (7-C),

2845 (C–H), 1650 (C᎐C); δ (CDCl ) 1.47–2.39 (14 H, m,

᎐

H

3

123.7 (4-CH᎐), 124.0 (3-CH᎐); (cis): 20.0 (CH ), 23.2 (CH ),

᎐

2

7 × CH₂), 3.63–4.54 (6 H, 3.63, d, J 2, CHOH(trans), 3.88–4.00,

m, OCH₂CH₂O, 4.00–4.07, m, CHOH(cis), 4.20–4.24, m,

CHOH(trans), 4.54, d, J 2, CHOH(cis)), 5.47–5.61 (2 H, m

25.8 (CH₂), 29.8 (CH₂), 30.0 (CH₂), 30.7 (CH₂), 42.4 (6-C),

63.5 and 65.0 (OCH₂CH₂O), 76.9 (CHOH), 113.6 (7-C), 122.3

(4-CH᎐), 124.6 (3-CH᎐); m/z (EI) 224 (M⁺, 8%), 224 (5), 205

᎐

2 × CH᎐); δ (CDCl ) (cis/trans) 21.1 (CH ), 21.2 (CH ), 21.8

᎐

C

3

2

(22), 162 (70), 144 (39), 134 (30), 99 (100), 86 (53), 73 (50), 55

(61).

(CH₂), 21.9 (CH₂), 25.3 (CH₂), 26.8 (CH₂), 27.7 (CH₂), 20.2

(CH₂), 30.8 (CH₂), 31.0 (CH₂), 31.3 (CH₂), 31.4 (CH₂), 32.8

(CH₂), 32.9 (CH₂), 45.8 and 45.9 (2 × 6-C), 63.5, 63.7, 64.0

and 64.4 (2 × OCH₂CH₂O), 68.6 and 70.4 (2 × CHOH), 115.9

cis-7,7-Ethylenedioxyspiro[5.5]undec-3-en-1-ol 28b

When the RCM reaction was repeated following the procedure

described above with epimerically pure alcohol 10b the corre-

sponding cis product 28b was obtained as a colourless oil

(93%), R_f0.32. HRMS: M 224.1417. C₁₃H₂₀O₃requires

224.1412. ν_max(ﬁlm)/cm^Ϫ13495 (C–OH), 2940, 2890 (C–H),

and 116.2 (2 × 7-C), 122.7, 124.1, 124.8 and 125.3 (2 × 3-CH᎐,

᎐

2 × 2-CH᎐); m/z (EI) 238 (M⁺, 60%), 219 (17), 181 (14), 167

᎐

(12), 99 (100), 86 (13), 55 (12).

trans- and cis-8,8-Ethylenedioxyspiro[6.6]tridec-4-en-1-ol 32a

and 32b

1620 (C᎐C); δ (CDCl ) 1.31–2.37 (12 H, m, 6 × CH ), 3.83–

᎐

H

3

2

4.01 (4 H, m, OCH₂CH₂O), 4.07 (1 H, d, J 3, CHOH), 4.20

(1 H, s, CHOH), 5.44–5.51 (1 H, m, CH᎐), 5.56–5.64 (1 H,

The RCM reaction was carried out following the procedure

described above with a mixture of the alcohols 14a and 14b

(1 : 1) and 5 mol% Ru()-catalyst at 30 ЊC for 0.5 h. The

product on ﬂash chromatography was separated into the two

epimeric alcohols 32a and 32b. Compound 32b was eluted

ﬁrst.

᎐

m, CH᎐); δ (CDCl ) 20.0 (CH ), 23.2 (CH ), 25.8 (CH ), 29.8

᎐

C

3

2

(CH₂), 30.0 (CH₂), 30.7 (CH₂), 42.4 (6-C), 63.5 and 65.0

(OCH CH O), 67.9 (CHOH), 113.6 (7-C), 122.3 (4-CH᎐), 124.6

᎐

2

(3-CH᎐); m/z (EI) 224 (M⁺, 4%), 205 (10), 162 (20), 144 (10),

᎐

134 (13), 99 (100), 86 (21), 73 (14), 55 (17).

cis-1,1-Ethylenedioxyspiro[5.6]dodec-10-en-7-ol 29b

cis-8,8-Ethylenedioxyspiro[6.6]tridec-4-en-1-ol 32b. A colour-

less oil (36%), R_f0.44. HRMS: M 252.1724. C₁₅H₂₄O₃requires

252.1725. ν_max(ﬁlm)/cm^Ϫ13490 (C–OH), 3001, 2930 (C–H),

Compound 29b was obtained following the procedure

described above from the alcohol epimer 11b using 5 mol%

Ru()-catalyst at 80 ЊC for 4 h. The product was a white crystal-

line solid (93%), mp 46 ЊC (Et₂O), R_f0.40 (Found: C, 70.29;

H, 9.21. C₁₄H₂₂O₃requires C, 70.58; H, 9.24%). HRMS:

M 238.1575. C₁₄H₂₂O₃requires 238.1568. ν_max(ﬁlm)/cm^Ϫ13480

1650 (C᎐C); δ (CDCl ) 1.35–1.99 (14 H, m, 7 × CH ), 2.60–

᎐

H

3

2

2.69 (2 H, m, CH₂), 3.89–3.99 (4 H, m, OCH₂CH₂O), 4.26

(1 H, d, J 3, CHOH), 4.32 (1 H, d, J 3, CHOH), 5.51–5.55 (1 H,

m, CH᎐), 5.77–5.79 (1 H, m, CH᎐); δ (CDCl ) 21.0 (CH ),

᎐

C

3

2

(O–H), 3000, 2910, 2860 (C–H), 1510 (C᎐C); δ (CDCl ) 1.98–

21.2 (CH₂), 21.6 (CH₂), 26.5 (CH₂), 26.9 (CH₂), 28.1 (CH₂),

29.9 (CH₂), 32.5 (CH₂), 48.5 (7-C), 63.5 and 64.5 (OCH₂CH₂O),

᎐

H

3

1.87 (11 H, m, 1 H from CH₂, 5 × CH₂), 1.98–2.06 (1 H, dd,

J 15, 9, from CH₂), 2.61–2.68 (1 H, m, CH₂), 2.73–2.81 (1 H,

m, from CH₂), 3.88–4.02 (4 H, m, OCH₂CH₂O), 4.12 (1H,

72.6 (CHOH), 116.5 (8-C), 128.4 (5-CH᎐), 132.7 (4-CH᎐);

᎐

m/z (EI) 252 (M⁺, 29%), 209 (51), 155 (30), 113 (21), 99 (100), 55

s, CHOH), 4.32 (1 H, s, CHOH), 5.49–5.56 (1 H, m, CH᎐),

(14).

᎐

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

1469

View Article Online

trans-8,8-Ethylenedioxyspiro[6.6]tridec-4-en-1-ol 32a.

A

(1-C᎐O); m/z (EI) 222 (M⁺, 3%), 194 (3), 112 (22), 99 (100), 79

(9), 55 (14).

᎐

colourless oil (34%), R_f0.31. HRMS: M 252.1732. C₁₅H₂₄O₃

requires 252.1725. ν_max(ﬁlm)/cm^Ϫ13500 (C–OH), 3008, 2930,

2840 (C–H), 1645 (C᎐C); δ (CDCl ) 1.51–1.73 (12 H, 6 × CH ),

2.08–2.13 (4 H, m, 2 × CH₂), 3.84–4.05 (5 H, m, 1 H from

CHOH, 4 H from OCH₂CH₂O), 4.24 (1 H, s, CHOH), 5.55–

᎐

H

3

2

6,6-Ethylenedioxyspiro[4.5]dec-2-en-1-one 36

Compound 36 was obtained from ketone 18 (0.78 mmol) using

5 mol% Ru()-catalyst at 75 ЊC for 2 h. The product was a white

crystalline solid (78%), R_f0.52, mp 95–95.3 ЊC (sublimation at

70 ЊC/0.5 mmHg) (Found: C, 69.56; H, 7.79. C₁₂H₁₆O₃requires

C, 69.23; H, 7.69%). HRMS: M 208.1090. C₁₂H₁₆O₃requires

5.61 (1 H, m CH᎐), 5.74–5.79 (1 H, m, CH᎐); δ (CDCl )

᎐

C

3

20.9 (CH₂), 21.9 (CH₂), 23.9 (CH₂), 26.3 (CH₂), 27.8 (CH₂),

30.2 (CH₂), 30.4 (CH₂), 31.7 (CH₂), 49.3 (7-C), 63.6 and 63.9

(OCH CH O), 76.2 (CHOH), 117.8 (8-C), 127.5 (5-CH᎐), 132.3

᎐

2

208.1099. ν_max(KBr)/cm^Ϫ12920, 2860 (C–H), 1680 (C᎐O), 1600

(4-CH᎐); m/z (EI) 252 (M⁺, 35%), 209 (55), 155 (30), 113 (26),

᎐

(C᎐C); δ (CDCl ) 1.20–1.98 (8 H, m, 4 × CH ), 2.23–2.35

᎐

H

3

2

99 (100), 55 (7).

(1 H, dt, J 19, 2, CH CH᎐CH), 2.81–2.93 (1 H, dt, J 19, 2,

᎐

2

CH CH᎐CH), 3.72–3.92 (4 H, m, OCH CH O), 5.99–6.03 (1 H,

᎐

2

6,6-Ethylenedioxyspiro[4.4]non-2-en-1-one 33

dt, J 6, 2, CH᎐), 7.54–7.60 (1 H, m, CH᎐); δ (CDCl ) 20.7

᎐

C

3

Bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride

(13 mg, 0.016 mmol) in dry toluene (1 ml), was added to a

solution of the ketone 15 (0.150 g, 0.67 mmol) in dry toluene

(20 ml) under argon. The mixture was stirred and heated at

70 ЊC for 2 h when another portion of bis(tricyclohexyl-

phosphine)(benzylidene)ruthenium dichloride (13 mg, 0.016

mmol) in dry toluene (1 ml) was added. The heating under

argon was continued at 70 ЊC for 2 h. The cold reaction mixture

was ﬁltered, the ﬁltrate evaporated and the residual material

subjected to ﬂash chromatography using CH₂Cl₂–EtOAc 8 : 1.

The product was a colourless oil (91%), R_f0.37 (Found: C,

68.23; H, 7.49. C₁₁H₁₄O₃requires C, 68.04; H, 7.21%). HRMS:

M 194.0948. C₁₁H₁₄O₃requires 194.0942. ν_max(ﬁlm)/cm^Ϫ13005,

(CH₂), 23.1 (CH₂), 31.9 (CH₂), 33.7 (CH₂), 40.4 (CH₂), 53.7

(5-C), 64.4 and 65.2 (OCH CH O), 110.7 (6-C), 133.1 (3-CH᎐),

᎐

2

162.2 (2-CH᎐), 210.1 (1-C᎐O); m/z (EI) 208 (M⁺, 24%), 163

᎐

(14), 125 (35), 111 (32), 99 (100), 83 (36), 71 (47), 57 (100).

7,7-Ethylenedioxyspiro[5.5]undec-3-en-1-one 37

Compound 37 was obtained from ketone 19 (0.60 mmol) and

5 mol% Ru()-catalyst at 30 ЊC for 0.5 h. The product was a

colourless oil (91%), R_f0.53 (Found: C, 70.54; H, 8.33.

C₁₃H₁₈O₃requires C, 70.27; H, 8.10%). HRMS: M 222.1250.

C₁₃H₁₈O₃requires 222.1255. ν_max(ﬁlm)/cm^Ϫ13005, 2908, 2860

(C–H), 1700 (C᎐O), 1460 (C᎐C); δ (CDCl ) 1.04–1.09 (1 H,

᎐

H

3

m, from CH₂), 1.38–1.63 (5 H, m, 2 × CH₂, 1 H from CH₂),

2.01–2.11 (1 H, m, from CH₂), 2.15–2.28 (2 H, m, CH₂), 2.52–

2.60 (1 H, m, from CH₂), 2.70–2.95 (2 H, m, CH₂), 3.75–4.00

2965, 2885 (C–H), 1705 (C᎐O), 1634 (C᎐C); δ (CDCl )

᎐

H

3

1.62–1.94 (4 H, m, 2 CH₂), 2.01–2.13 (2 H, m, CH₂), 2.29–2.40

(1 H, dt, J 19, 2, CH CH᎐CH), 2.95–3.03 (1 H, dt, J 19, 2,

᎐

2

(4 H, m, OCH CH O), 5.52–5.58 (1 H, m, CH᎐), 5.64–5.68

᎐

CH CH᎐CH), 3.77–3.90 (4 H, m, OCH CH O), 6.03–6.06 (1 H,

2

᎐

2

(1 H, m, CH᎐); δ (CDCl ) 21.7 (CH ), 23.3 (CH ), 31.6 (CH ),

᎐

dt, J 6, 2, CH᎐), 7.59–7.63 (1 H, m, CH᎐); δ (CDCl ) 19.0

C

3

2

᎐

C

3

33.0 (CH₂), 33.3 (CH₂), 40.3 (CH₂), 55.9 (6-C), 63.9 and 65.4

(CH₂), 33.4 (CH₂), 34.2 (CH₂), 39.1 (CH₂), 57.9 (5-C), 64.5 and

(OCH CH O), 110.3 (7-C), 122.8 (4-CH᎐), 125.3 (3-CH᎐),

᎐

65.3 (OCH CH O), 118.8 (6-C), 133.1 (3-CH᎐), 162.7 (2-CH᎐),

2

᎐

2

210.0 (1-C᎐O); m/z (EI) 222 (M⁺, 14%), 177 (25), 160 (80), 133

210.1 (1-C᎐O); m/z (EI) 194 (M⁺, 9%), 137 (7), 99 (100), 79 (8),

᎐

(32), 112 (32), 99 (100), 86 (27), 55 (37).

66 (7), 55 (14).

1,1-Ethylenedioxyspiro[5.6]dodec-10-en-7-one 38

1,1-Ethylenedioxyspiro[4.5]dec-8-en-6-one 34

Compound 38 was obtained from ketone 20 (0.60 mmol) using

5 mol% Ru()-catalyst at 60 ЊC for 4 h. The product was a

colourless oil (86%), R_f0.55 (Found: C, 70.94; H, 8.76.

C₁₄H₂₀O₃requires C, 71.18; H, 8.47%). HRMS: M 236.1409.

C₁₄H₂₀O₃requires 236.1412. ν_max(ﬁlm)/cm^Ϫ13005, 2920,

2840 (C–H), 1690 (C᎐O), 1590 (C᎐C); δ (CDCl ) 1.36–2.31

Compound 34 was prepared following the procedure described

above from ketone 16 (0.42 mmol) using 5 mol% Ru()-catalyst

at 30 ЊC for 4 h. The product was a colourless oil (89%), R_f

0.53 (Found: C, 69.47; H, 7.89. C₁₂H₁₆O₃requires C, 69.23; H,

7.69%). HRMS: M 208.1106. C₁₂H₁₆O₃requires 208.1099.

ν_max(ﬁlm)/cm^Ϫ13009, 2910, 2870 (C–H), 1700 (C᎐O), 1655

᎐

H

3

᎐

(12 H, m, 6 × CH₂), 2.50–2.60 (2 H, m, CH₂), 3.77–3.90 (4 H,

(C᎐C); δ (CDCl ) 1.19–1.31 (1 H, m, from CH ), 1.48–1.82

᎐

H

3

2

m, OCH CH O), 5.43–5.48 (1 H, m, CH᎐), 5.56–5.60 (1 H, m,

(4 H, m, 2 × CH₂), 2.10–2.18 (1 H, m, from CH₂), 2.37–2.44

(1 H, m, from CH₂), 2.62–2.69 (1 H, dd, J 18, 5, CH₂), 2.71–2.79

(1 H, m, from CH₂), 2.95–3.03 (1 H, m, from CH₂), 3.75–3.90

᎐

2

CH᎐); δ (CDCl ) 20.8 (CH ), 22.9 (CH ), 27.1 (CH ), 28.6

᎐

C

3

2

(CH₂), 29.4 (CH₂), 31.4 (CH₂), 39.2 (CH₂), 61.7 (7-C), 64.3 and

64.7 (OCH CH O), 111.0 (8-C), 125.7 (5-CH᎐), 129.8 (4-CH᎐),

(4 H, m, OCH CH O), 5.57–5.64 (1 H, m, CH᎐), 5.69–5.76

᎐

2

᎐

2

214.4 (1-C᎐O); m/z (EI) 236 (M⁺, 40%), 191 (14), 125 (17), 112

(1 H, m, CH᎐); δ (CDCl ) 19.6 (CH ), 33.4 (CH ), 33.5 (CH ),

᎐

C

3

2

(16), 99 (100), 86 (43), 79 (24), 55 (29).

36.1 (CH₂), 40.3 (CH₂), 58.1 (6-C), 64.7 and 65.0 (OCH₂CH₂O),

117.8 (7-C), 123.7 (4-CH᎐), 126.0 (3-CH᎐), 210.1 (1-C᎐O);

᎐

m/z (EI) 208 (M⁺, 29%), 137 (6), 99 (100), 79 (15), 55 (14).

6,6-Ethylenedioxyspiro[4.6]undec-2-en-1-one 39

Compound 39 was obtained following the procedure described

above from ketone 21 (40 mmol) using 5 mol% Ru()-catalyst

at 75 ЊC for 4 h. The product was a colourless oil (86%), R_f0.46

(Found: C, 70.49; H, 8.38. C₁₃H₁₈O₃requires C, 70.27; H,

8.10%). HRMS: M 222.1256. C₁₃H₁₈O₃requires 222.1255.

1,1-Ethylenedioxyspiro[4.6]undec-9-en-6-one 35

Compound 35 was obtained from ketone 17 (0.80 mmol) using

5 mol% Ru()-catalyst at 60 ЊC for 4 h. The product was a

colourless oil (89%), R_f0.57 (Found: C, 70.49; H, 8.41.

C₁₃H₁₈O₃requires C, 70.27; H, 8.10%). HRMS: M 222.1257.

C₁₃H₁₈O₃requires 222.1255. ν_max(ﬁlm)/cm^Ϫ13000, 2940, 2885

ν_max(ﬁlm)/cm^Ϫ13003, 2910, 2880 (C–H), 1700 (C᎐O), 1610

᎐

(C᎐C); δ (CDCl ) 1.47–1.84 (9 H, m, 4 × CH , 1 H from CH ),

᎐

H

3

2

(C–H), 1695 (C᎐O), 1645 (C᎐C); δ (CDCl ) 1.37–1.83 (5 H, m,

2.13–2.18 (1 H, m, from CH₂), 2.34–2.42 (1 H, dt, J 19, 2,

CH CH᎐CH), 2.86–2.93 (1 H, dt, J 19, 2, CH CH᎐CH), 3.77–

᎐

H

3

1 H from CH₂, 2 × CH₂), 1.98–2.10 (1 H, dd, J 15, 8.5, from

CH₂), 2.23–2.48 (4 H, m, 2 × CH₂), 2.82–2.95 (1 H, m, from

CH₂), 3.20–3.35 (1 H, m, from CH₂), 3.78–3.91 (4 H, m,

᎐

2

3.90 (4 H, m, OCH CH O), 5.98–6.01 (1 H, m, CH᎐), 7.54–7.58

᎐

2

(1 H, m, CH᎐); δ (CDCl ) 21.4 (CH ), 22.8 (CH ), 27.6 (CH ),

᎐

C

3

2

OCH CH O), 5.38–5.46 (1 H, m, CH᎐), 5.57–5.72 (1 H, m,

33.5 (CH₂), 35.2 (CH₂), 40.5 (CH₂), 56.8 (5-C), 64.2 and 64.3

᎐

2

CH᎐); δ (CDCl ) 19.4 (CH ), 28.4 (CH ), 29.0 (CH ), 32.1

(OCH CH O), 113.3 (6-C), 132.6 (3-CH᎐), 162.2 (2-CH᎐),

᎐ ᎐

2 2

᎐

C

3

2

(CH₂), 34.5 (CH₂), 38.8 (CH₂), 64.5 and 65.0 (OCH₂CH₂O),

65.7 (7-C), 118.4 (8-C), 126.3 (5-CH᎐), 129.4 (4-CH᎐), 213.7

210.8 (1-C᎐O); m/z (EI) 222 (M⁺, 12%), 113 (27), 99 (100), 86

᎐

(7), 55 (11).

᎐

1470

J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

View Article Online

7,7-Ethylenedioxyspiro[5.6]dodec-3-en-1-one 40

3.31–3.95 (4 H, m, OCH₂CH₂O), 5.62–5.64 (1 H, d, J 5,

HCOOCPhNO2), 5.69–5.76 (1 H, m, CH᎐), 5.88–5.94 (1 H, m,

᎐

Compound 40 was obtained following the procedure described

above from ketone 22 (0.38 mmol) and 5 mol% Ru()-catalyst.

The product was a colourless oil (87%), R_f0.43 (Found: C,

71.41; H, 8.20. C₁₄H₂₀O₃requires C, 71.18; H, 8.47%). HRMS:

M 236.1421. C₁₄H₂₀O₃requires 236.1412. ν_max(ﬁlm)/cm^Ϫ13003,

CH᎐), 8.19–8.27 (4 H, m, 4 × CH ); δ (CDCl ) 17.8 (CH ),

᎐

Ar

C

3

2

21.3 (CH₂), 27.1 (CH₂), 27.6 (CH₂), 31.3 (CH₂), 34.3 (CH₂),

49.7 (7-C), 63.5 and 64.2 (OCH₂CH₂O), 76.7 (1-HCOOCPh),

119.1 (8-C), 123.6 (2 × CH_Ar), 128.6 (5-CH᎐), 130.6 (2 × CH_Ar),

᎐

132.8 (4-CH᎐), 136.4 (CNO ), 150.4 (CH᎐C CO ), 163.4

᎐

Ar

2

2945, 2860 (C–H), 1700 (C᎐O), 1610 (C᎐C); δ (CDCl ) 1.38–

᎐

(C᎐O, ester); m/z (EI) 373 (M⁺, 56%), 330 (5), 290 (11), 223 (24),

H

3

᎐

1.72 (8 H, m, 4 × CH₂), 1.94–1.98 (1 H, m, from CH₂), 2.18–

2.30 (2 H, m, CH₂), 2.48–2.57 (1 H, m, from CH₂), 2.82–2.85

(2 H, m, CH₂), 3.79–3.93 (4 H, m, OCH₂CH₂O), 5.58–5.64

207 (54), 150 (14), 99 (100), 55 (6).

The structure has been conﬁrmed by a single crystal X-ray

analysis (Fig. 2).

(1 H, m, CH᎐), 5.68–5.75 (1 H, m, CH᎐); δ (CDCl ) 20.6 (CH ),

᎐

C

3

2

22.0 (CH₂), 27.0 (CH₂), 32.1 (CH₂), 33.3 (CH₂), 33.7 (CH₂),

40.8 (CH₂), 58.2 (6-C), 64.1 and 64.3 (OCH₂CH₂O), 113.2

cis-7,7-Ethylenedioxyspiro[5.5]undec-3-en-1-yl p-nitrobenzoate

44

(7-C), 123.0 (4-CH᎐), 126.4 (3-CH᎐), 210.7 (1-C᎐O); m/z (EI)

᎐

236 (M⁺, 29%), 208 (7), 191 (10), 174 (46), 151 (35), 137 (20),

99 (100), 79 (15), 55 (12).

Compound 44 was obtained following the procedure described

above from the alcohol 28b as a crystalline solid (84%), R_f0.46,

mp 142–142.5 ЊC (Et₂O). HRMS: M 373.1516. C₂₀H₂₃NO₆

requires 373.1525. ν_max(KBr)/cm^Ϫ12920, 2890 (C–H), 1705

8,8-Ethylenedioxyspiro[6.6]tridec-3-en-1-one 41

(C᎐O), 1510, 1350 (NO , CH᎐CH ); δ (CDCl ) 1.38–1.75

᎐

2

Ar

H

3

Compound 41 was obtained from ketone 23 (0.45 mmol) using

5 mol% Ru()-catalyst at 75 ЊC for 2 h. The product was

a colourless oil (94%), R_f0.51 (Found: C, 72.26; H, 8.61.

C₁₅H₂₂O₃requires C, 72; H, 8.80%). HRMS: M 250.1561.

C₁₅H₂₂O₃requires 250.1569. ν_max(ﬁlm)/cm^Ϫ13003, 2960, 2840

(8 H, m, 4 × CH₂), 2.06–2.20 (2 H, m, CH₂), 2.39–2.46 (1 H,

m, from CH₂), 2.59–2.67 (1 H, m, from CH₂), 3.45–3.54 (1 H,

m, OCH₂CH₂O), 3.71–3.81 (3 H, m, OCH₂CH₂O), 5.49–5.52

(1 H, m, CH᎐), 5.69 (1 H, s, HCOOCPhNO₂), 5.73–5.78 (1 H,

᎐

m, CH᎐), 8.14–8.24 (4 H, m, 4 × CH ); δ (CDCl ) 20.2 (CH ),

᎐

Ar

C

3

2

(C–H), 1705 (C᎐O), 1631 (C᎐C); δ (CDCl ) 1.41–1.67 (8 H,

᎐

H

3

23.1 (CH₂), 26.3 (CH₂), 29.0 (CH₂), 30.2 (CH₂), 30.7 (CH₂),

42.8 (6-C), 63.6 and 64.7 (OCH₂CH₂O), 71.4 (1-HCOOCPh),

m, 4 × CH₂), 1.98–2.06 (2 H, m, CH₂), 2.21–2.44 (4 H, m,

2 × CH₂), 2.84–2.85 (1 H, m, from CH₂), 3.41–3.51 (1 H, m,

from CH₂), 3.79–3.90 (4 H, m, OCH₂CH₂O), 5.47–5.52 (1 H,

111.7 (7-C), 121.5 (4-CH᎐), 123.4 (2 × CH ), 125.7 (3-CH᎐),

᎐

Ar

130.7 (2 × CH ), 136.9 (CNO ), 150.3 (CH᎐C CO ), 164.2

᎐

Ar

2

Ar

2

m, CH᎐), 5.58–5.62 (1 H, m, CH᎐); δ (CDCl ) 22.5 (CH ),

᎐

(C᎐O, ester); m/z (EI) 373 (M⁺, 15%), 223 (10), 207 (77),

C

3

2

᎐

22.6 (CH₂), 27.30 (CH₂), 29.0 (CH₂), 29.7 (CH₂), 31.0 (CH₂),

33.3 (CH₂), 39.9 (CH₂), 63.5 (OCH₂CH₂O), 64.5 (7-C), 64.6

144 (65), 117 (30), 104 (37), 99 (100), 91 (79), 73 (43), 55 (27).

The structure has been conﬁrmed by a single crystal X-ray

analysis (Fig. 3).

(OCH CH O), 113.4 (8-C), 126.2 (5-CH᎐), 129.6 (4-CH᎐),

᎐

2

215.0 (1-C᎐O); m/z (EI) 250 (M⁺, 65%), 165 (12), 141 (15), 125

᎐

(5), 99 (100), 86 (13), 55 (12).

cis-1,1-Ethylenedioxyspiro[5.6]dodec-10-en-7-yl p-nitrobenzoate

45

cis-1,1-Ethylenedioxyspiro[4.5]dec-8-en-6-yl p-nitrobenzoate 42

Compound 45 was obtained following the procedure described

above from the alcohol 29b as a crystalline solid (75%), R_f0.37,

mp 114.2–114.5 ЊC (Et₂O). HRMS: M 387.1674. C₂₁H₂₅NO₆

requires 387.1681. ν_max(KBr)/cm^Ϫ12940, 2890 (C–H), 1713

A mixture of p-nitrobenzoyl chloride (0.256 g, 1.42 mmol), the

alcohol 25b (0.100 g, 0.47 mmol) and DMAP (0.175 g, 1.42

mmol) in dry CH₂Cl₂(7 ml) was stirred at ambient temperature

for 15 h when TLC monitoring showed that the reaction had

gone to completion. The solvent was distilled oﬀ and the crude

product puriﬁed by ﬂash chromatography using hexane–EtOAc

5 : 1, R_f0.36. The product was a pale yellow crystalline material

(0.152 g, 89%), mp 131 ЊC (Et₂O). HRMS: M 359.1368.

C₁₉H₂₁NO₆requires 359.1368. ν_max(KBr)/cm^Ϫ12960, 2840

(C᎐O), 1530, 1355 (NO , CH᎐CH ); δ (CDCl ) 1.44–1.92

᎐

2

Ar

H

3

(11 H, m, 5 × CH₂, 1 H from CH₂), 2.26–2.34 (2 H, m, CH₂),

2.95–3.02 (1 H, m, from CH₂), 3.41–3.48 (1 H, m, 1 H from

OCH₂CH₂O), 3.71–3.81 (3 H, m, 3 H from OCH₂CH₂O),

5.66–6.00 (3 H, m, 2 H from CH᎐, 1 H from HCOOCPh-

᎐

NO₂), 8.16–8.33 (4 H, m, 4 × CH_Ar); δ_C(CDCl₃) 20.1 (CH₂),

21.6 (CH₂), 23.2 (CH₂), 25.2 (CH₂), 26.7 (CH₂), 29.9 (CH₂),

30.3 (CH₂), 45.1 (7-C), 63.5 and 64.3 (OCH₂CH₂O), 76.1

(C–H), 1710 (C᎐O), 1450 (NO ); δ (CDCl ) 1.56–2.01 (7 H,

᎐

2

H

3

m, 3 × CH₂, 1 H from CH₂), 2.32 (2 H, s, CH₂), 2.75–2.81 (1 H,

d, J 18, from CH₂), 3.38–3.42 (1 H, m, from OCH₂CH₂O),

3.67–3.80 (3 H, m, OCH₂CH₂O), 5.48 (1 H, s, HCOOCPhNO₂),

(HCOOCPh), 112.6 (8-C), 123.5 (2 × CH ), 128.0 (5-CH᎐),

᎐

Ar

130.7 (2 × CH ), 131.9 (4-C), 136.8 (CNO ), 150.4 (CH᎐C -

᎐

Ar

2

5.53–5.57 (1 H, m, CH᎐), 5.72–5.78 (1 H, m, CH᎐), 8.16–8.28

᎐

CO ), 163.7 (C᎐O, ester); m/z (EI) 387 (M⁺, 63%), 237 (42), 221

᎐

2

(4 H, m, 4 × CH_Ar); δ_C(CDCl₃) 17.3 (CH₂), 28.0 (CH₂), 29.4

(CH₂), 31.6 (CH₂), 34.0 (CH₂), 46.7 (6-C), 63.9 and 64.6

(OCH₂CH₂O), 71.7 (1-H COOCPh), 118.0 (7-C), 122.4

(100), 192 (25), 150 (34), 125 (52), 99 (86), 55 (16).

The structure has been conﬁrmed by a single crystal X-ray

analysis (Fig. 4).

(4-CH᎐), 123.45 (CH ), 123.52 (CH ), 125.3 (3-CH᎐), 130.6

᎐

Ar

(CH ), 130.7 (CH ), 136.4 (CNO ), 150.4 (CH᎐C CO ),

᎐

Ar

2

Ar

2

165.2 (C᎐O, ester); m/z (EI) 359 (M⁺, 5%), 209 (5), 193 (55), 150

References

᎐

(50), 131 (100), 104 (57), 99 (100), 91 (36), 55 (60).

The structure has been conﬁrmed by a single crystal X-ray

analysis (Fig. 1).

1 P. S. Aburel and K. Undheim, J. Chem. Soc., Perkin Trans. 1, 2000,

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2 P. S. Aburel, C. Rømming and K. Undheim, J. Chem. Soc., Perkin

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cis-1,1-Ethylenedioxyspiro[4.6]undec-9-en-6-yl p-nitrobenzoate

43

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Compound 43 was obtained following the procedure described

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J. Chem. Soc., Perkin Trans. 1, 2001, 1458–1472

Article Doi

Synthesis of α-hydroxy and α-oxospiranes through ruthenium(II)-catalyzed ring-closing metathesis

DOI: 10.1039/b101462p

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Full text of DOI:10.1039/b101462p

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