ROM-RCM of cycloalkene-yne

Tetrahedron 60 (2004) 7375–7389

Tsuyoshi Kitamura,^aYuichi Kuzuba,^aYoshihiro Sato,^aHideaki Wakamatsu,^bReiko Fujita^b

and Miwako Mori^a

,

*

^aGraduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan

^bTohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan

Received 25 March 2004; revised 12 May 2004; accepted 14 May 2004

Available online 24 June 2004

We dedicate this paper to Professor Grubbs on the occasion of his receipt of the Tetrahedron Prize

Abstract—Ring-opening metathesis and ring-closing metathesis (ROM-RCM) of cycloalkene-yne was demonstrated using a ﬁrst- or

second-generation ruthenium complex. When cycloalkenes bearing the alkyne part at the C-3 position were reacted with a ﬁrst-generation

ruthenium–carbene complex under an atmosphere of ethylene, ROM-RCM proceeded smoothly to give skeletal reorganized products in

good yields. In this reaction, cycloalkene-ynes having terminal alkyne were suitable. On the other hand, when cycloalkenes bearing the

alkyne part at the C-1 position were treated with a second-generation ruthenium–carbene complex, ROM-RCM proceeded smoothly to give

bicyclic compounds and/or dimeric compounds in good yields.

1. Introduction

The metathesis reaction of cycloalkene did not proceed

under the usual reaction conditions, and cyclooctene or

norbonene afforded a polymer via ring opening polymeri-

zation (ROMP). Recently, ring-opening metathesis of

cycloalkene followed by cross-metathesis (ROM-CM⁶)

with oleﬁn has been developed.

Transition metals have played an important role in recent

synthetic organic chemistry, and they are now important

tools for the syntheses of complex molecules, such as

natural products and biologically active substances. Oleﬁn

metathesis reaction¹using a metal carbene complex is

interesting because formally the carbon–carbon double

bonds are cleaved and, at the same time, new carbon–

carbon double bonds are formed between the two double

bonds. Intramolecular oleﬁn metathesis is a useful method-

ology in synthetic organic chemistry, since carbocyclic and

heterocyclic compounds having various ring sizes can be

synthesized. In 1999, second-generation ruthenium–car-

bene complexes², such as 1b and 1c, were developed by

Herrmann, Nolan and Grubbs, independently, and meta-

thesis of oleﬁn having substituents could be further

developed. On the other hand, intramolecular enyne

metathesis^3–5is particularly attractive since the double

bond of enyne is cleaved and the alkylidene part of alkene

migrates to the alkyne carbon to give a cyclized compound

having a diene moiety. We have already reported intra-

molecular enyne metathesis³using Grubbs’ ruthenium

carbene complex 1 and the syntheses of ﬁve- to nine-

membered ring compounds.

Keywords: Enyne metathesis; Ring-opening metathesis and ring-closing

metathesis; ROM-RCM; Cycloalkene-yne; Pyrrole derivative; Ethylene.

*

Corresponding author. Tel./fax: þ81-11-706-4982;

e-mail address: mori@pharm.hokudai.ac.jp

Scheme 1. Metathesis reaction of alkene.

doi:10.1016/j.tet.2004.05.030

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T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

Ring-opening metathesis and ring-closing metathesis⁷

(ROM-RCM) of cycloalkene-yne is also very attractive,

but there have been few reports on ROM-RCM in the

literature.⁸Herein, we describe in detail of ROM-RCM

of cycloalkene-ynes I and II using ruthenium–carbene

complex 1 (Scheme 1).^3a,b

2. Results and discussion

2.1. Metathesis of cycloalkene having alkyne in a tether

at the C-3 position

Metathesis of cycloalkene-yne, whose tether having an

alkyne part is connected to the C-3 position of cycloalkene,

was investigated. If the alkyne part of substrate I reacts with

a ruthenium complex, ruthenacyclobutene III should be

formed and it would be converted into ruthenium–carbene

complex IV by ring-opening. Then, if this carbene complex

IV reacts with a cycloalkene part intramolecularly, highly

strained ruthenium complex V would be formed and it

should be converted into VI. However, this ruthenium

carbene complex VI cannot react with the diene moiety

intramolecularly and would react with another molecule I to

give a polymer (Scheme 2).

Scheme 3. Synthesis cycloalkene-yne 2.

quantitative yields. N-Alkylation of N-cycloheptenyl- or

N-cyclooctenyl-N-tosylamides 3c¹⁰and 3d^7cwith but-2-

ynyl methanesulfonate or propargyl bromide gave cyclo-

alkene-ynes 2b, 2e, 2c and 2f, respectively, in good yields.

Scheme 4. ROM-RCM of cycloalkene-yne 2b.

When a CH₂Cl₂solution of cycloheptene-yne 2b and

10 mol% of ruthenium complex 1a was stirred at room

temperature for 24 h under an atmosphere of ethylene, we

were pleased to ﬁnd that the desired ring-opening metathesis

product 4b was obtained in 56% yield (Scheme 4). This

product 4b should be obtained through the proposed

reaction course. Thus, formally, in this reaction, the double

bond of cycloalkene was cleaved, and one alkylidene carbon

reacts with an alkyne carbon to form a ﬁve-membered ring,

while the other alkylidene carbon and alkyne carbon react

with methylene parts of ethylene. It is interesting that three

new double bonds in 4b were formed from two double

bonds and one triple bond in 2b in this process. As

substrates, 2a and 2c were treated in a similar manner, and

the desired ROM-RCM products 4a and 4c were obtained in

15 and 22% yields, respectively, and the starting materials

2a and 2c were recovered in 70 and 75% yields, respectively

(Table 1, runs 1 and 3).

Scheme 2. Our plan for ROM-RCM of cycloalkene-yne I.

However, if this reaction were carried out under an

atmosphere of ethylene,^3f,9ruthenium complex VI would

react with ethylene to give ring-opening metathesis product

VIII via ruthenacyclobutane VII. The chain lengths of the

tethers in the products VIII would be dependent on the ring-

size of cycloalkene.

To examine our plan, various cycloalkene-ynes 2 were

prepared as shown in Scheme 3. N-Alkylation of

N-2-butynyl- or N-propargyl-N-tosylamide 3a and 3b with

3-bromocyclohexene gave cyclohexene-ynes 2a and 2d in

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

7377

Table 1. ROM-RCM of cycloalkene-yne 2

metathesis product 8a of an alkyne part of 7a with ethylene.

Presumably, the steric hindrance between the intermediate

ruthenium–carbene part and the silyloxy group would

prevent the intramolecular metathesis reaction (Scheme 1).

As a result, the ruthenium–carbene part reacted with

ethylene to yield 1,3-diene 8a. On the other hand, when

cyclohexene-yne 7b having trans-substituents was treated

in a similar manner, the desired ring-opening metathesis

product 9b was obtained in 90% yield as a single product

(Scheme 6).

Run

R

n

Time (h)

Yield (%)

1

2

3

4

5

6

Me

H

1

2

3

1

2

3

2a

2b

2c

2d

2e

2f

24

4

1

4a,15

4b,56

4c,22

4d,78

4e,70

4f,75

Since this reaction was carried out under ethylene gas,

cycloalkene bearing terminal alkyne can be used.^3fWhen a

CH₂Cl₂solution of cyclohexene-yne 2d and 10 mol% of 1a

was stirred at room temperature under an atmosphere of

ethylene, the reaction proceeded smoothly and the desired

product 4d was obtained in 78% yield (run 4). Under similar

reaction conditions, metatheses of cycloalkene-ynes 2e and

2f were carried out and the desired products 4e and 4f were

obtained in good yields (runs 5 and 6).

Next, the ROM-RCM reaction of cycloalkene-yne 7 having

two substituents on the cycloalkene ring was investigated.

These cycloalkene-ynes 7 were synthesized from cyclo-

alkenes 5a or 5b as shown in Scheme 5. Cycloalkene-ynes

7a and 7c having cis-substituents were prepared using

palladium-catalyzed allylic substitution of carbonates 6a

and 6b. Cycloalkene-ynes 7b and 7d having trans-

substituents were prepared from 5a and 5b using Mitsunobu

reaction.

Scheme 6. ROM-RCM of cycloalkene-yne bearing substituents.

Since cyclized product 9b has the diene moiety and an

alkene part, cyclization by Diels–Alder reaction would be

expected (Scheme 7). Desilylation of 9b followed by Dess–

Martin oxidation¹¹at room temperature afforded a mixture

of the desired ketone 10 and tricyclic compound 11, which

should be produced by Diels–Alder reaction, in 86% yield.

The resultant mixture was allowed to stand at room

temperature to give tricyclic compound 11 as a single

product. The stereochemistry of 11 was determined by an

NOESY experiment, and the cross-peaks on NOE were

observed between the ring-junction protons. These results

Scheme 5. Synthesis of cycloalkene-yne 7 having substituents.

When a CH₂Cl₂solution of 7a having cis-substituents and

10 mol% of 1a was stirred at room temperature under an

atmosphere of ethylene, the reaction proceeded smoothly to

give a single product in high yield. However, this is a cross-

Scheme 7. Synthesis of tricyclic compound via Diels–Alder reaction.

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T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

indicated, that formally, tricyclic compound 11 was formed

via [2þ2þ2] cocyclization of cycloalkene, alkyne and

ethylene.

metathesis products 12g and 12h with ethylene in each case

(Scheme 9). It is not clear why the starting materials were

recovered without formation of ROM-RCM products.

Under similar reaction conditions, metatheses of cyclo-

pentene-ynes 7c and 7d were carried out. The reaction of

each compound having cis- or trans-substituents proceeded

smoothly to afford the desired products 9c and 9d,

respectively in good yields (Scheme 8). Presumably, steric

hindrance between the ruthenium–carbene part and the

silyloxy group on the cyclopentene ring in 7c is not affected

by ring-opening metathesis and the desired product 9c is

formed.

2.2. Metathesis of cycloalkene having alkyne in a tether

at the C-1 position

Subsequently, metathesis reaction of cycloalkene-yne,

whose tether having an alkyne part is connected to the

C-1 position of cycloalkene, was investigated (Scheme 10).

If the metathesis of cycloalkene-yne II proceeds under

ethylene gas, the alkyne part of II would react with the

ruthenium–carbene complex to give ruthenacyclobutene

XI, which would be converted into ruthenium–carbene

complex XII by ring opening. Intramolecular [2þ2]

cycloaddition would occur to afford ruthenacyclobutane

XIII, which would then be converted into ruthenium–

carbene complex XIV. This would react with ethylene

intermoleculary to afford triene IX. On the other hand, if

this complex XIV can react with an alkene part of the diene

moiety intramoleculary, bicyclic compound X would be

obtained.

Scheme 8. ROM-RCM of cycloalkene-ynes 7c and 7d.

Subsequently, the construction of a dehydropiperidine

skeleton was attempted. For that purpose, one carbon in a

tether of cycloalkene-yne should be elongated. Cyclo-

alkene-ynes 2g and 2h having one-carbon elongated tether

were synthesized from 3e and 3f by the usual method.

ROM-RCM of these cycloalkene-ynes 2g and 2h were

carried out in a similar manner, but, unfortunately, no ring-

opening metathesis products 4g or 4f were formed and the

starting materials 2g and 2h were recovered in 96 and 66%

yields, respectively, along with a small amount of cross-

Scheme 10. Plan for ROM-RCM of cycloalkene-ynes II.

Scheme 9. Attempt to synthesize piperidine-ring.

Scheme 11. Synthesis cycloalkene-yne 14.

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

7379

Cycloalkene-yne 14 was easily prepared from ester or

carboxylic acid 13 as shown in Scheme 11. Reduction of

13a, 13b or 13c¹²with DIBAL-H followed by bromination

afforded a corresponding allyl bromide, which was reacted

with propargyl amine followed by tosylation to afford

cycloalkene-yne 14a, 14b or 14c in moderate yield.

Synthesis of cycloalkene-yne 14d or 14e was carried out

by condensation of carboxylic acid 13d or 13e with

propargylamine followed by alkylation with benzyl

bromide.

When a CH₂Cl₂solution of cyclohexene-yne 14b and

10 mol% of a ﬁrst-generation ruthenium carbene complex

1a was stirred at room temperature for 18 h under an

atmosphere of ethylene, cross-enyne metathesis product 15b

was obtained in 76% yield instead of the ROM-RCM

product (Scheme 12). Presumably, carbene complex 16

cannot react with trisubstituted alkene moiety. A second-

generation ruthenium carbene complex was therefore used

for ROM-RCM of 14b.

Scheme 13. ROM-RCM of 14b using 1b.

and the yield of 5,7-fused ring compound 17a was greater

than that of 5,8-fused ring compound 17b.

Next, to examine whether dimeric compound 18b is

converted into a 5,7 or 5,8-fused ring compounds under

the metathesis reaction conditions, a solution of 18b and

20 mol% of 1b in toluene was stirred at 80 8C for 16 h under

an atmosphere of ethylene. Interestingly, 17a, 17b and 19b

were obtained in 39, 9 and 21% yields, respectively

(Scheme 14). In this case, the yield of 17a was also higher

than that of 17b. These results suggest that 18b reacted with

ethylene in the presence of ruthenium complex 1b to afford

19b and that 17a and 17b were then formed.

Scheme 12. Reaction of 14b with 1a.

When a toluene solution of 14b and 10 mol% of a second-

generation ruthenium carbene complex 1b was stirred at

80 8C for 16 h under an atmosphere of ethylene, two

products were obtained (Scheme 13). Surprisingly, the

1

expected products 17b and 19b were not obtained, and H

NMR and mass spectra revealed that one is compound 17a

having a 5,7-fused ring system, which was obtained in 46%

yield. The structure was conﬁrmed by X-ray crystallo-

graphic analysis.¹³The other is 16-membered ring

compound 18b, which was obtained in 4% yield. The

structure of 18b was conﬁrmed as follows. From the

1

coupling constant of Ha and Hb on a H NMR spectrum

(J_Ha–Hb¼16.0 Hz), this compound was ﬁrst thought to be

17b⁰having trans-oleﬁn because one set of peaks corre-

Scheme 14. ROM of dimeric compound 18b.

0

sponding to 17b were seen on H NMR and ¹³C NMR

spectra. However, a mass spectrum of 18b (m/z 606 [M^þ])

indicated that it is a dimeric compound, formed from

intermolecular metathesis of two molecules.

1

Since ring-closure of 19b into an eight-membered ring is

difﬁcult, oleﬁn migration¹⁴followed by oleﬁn metathesis

would occur to give 5,7-fused ring compound 17a.

Isomerization of the double bond of 19b should be caused

by a ruthenium complex. Coordination of the terminal oleﬁn

of 19b into a ruthenium complex followed by hydrogen

elimination and then reductive elimination gives 19b⁰via

20. Oleﬁn metathesis of 19b⁰affords 5,7-fused ring

compound 17a. At a higher reaction temperature, 17b was

When a solution of 14b and 10 mol% of 1b in CH₂Cl₂was

reﬂuxed under an atmosphere of ethylene for 24 h, the

yields were improved. Although the expected product 17b

was obtained in 14% yield under these reaction conditions,

the main product was dimeric compound 18b (57% yield)

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T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

Table 3. ROM-RCM of cycloalkene-yne 14c

Run

Conditions

Yields (%)

17a

36

Trace

0

18c

Scheme 15. Possible reaction course for formation of 17a.

1^a

2

Toluene, 80 8C, 21 h

CH₂Cl₂, reﬂux, 15 h

CH₂Cl₂, reﬂux, 1 h

8

58

80

not formed because 19b was easily converted into 19b⁰and

17a should be stable under these reaction conditions

(Scheme 15).

3

a

21 was obtained in 6% yield.

Subsequently, ROM-RCM of cyclopentene-yne 14a was

investigated (Table 2). When a CH₂Cl₂solution of 14a and

10 mol% of 1b was reﬂuxed under an atmosphere of

ethylene for 2 h, the desired ROM-RCM product 17a was

obtained in 95% yield (run 1). Even in the case of longer

reaction time (26 h), 17a was obtained in a quantitative

yield (run 2). The results indicated that ring-closure into a

seven-membered ring is easier and that 17a is stable under

these reaction conditions. The use of 5 mol% of 1b gave

similar results (run 3). In this reaction, ethylene was not

introduced into the product. Thus, the reaction was carried

out in the absence of ethylene to give 17a in 81% yield,

although the yield was slightly decreased (run 4).

.

for 15 h, dimerization product 18c was obtained in 58%

yield along with a considerable amount of 22 (run 2).

However, when the reaction was quenched after the spot of

the starting material 14c had disappeared on TLC, only 18c

was obtained in 80% yield (run 3).

ROM-RCM of 5-, 6-, and 7-membered cycloalkene-ynes 14

are summarized in Scheme 16. When the reaction was

carried out in CH₂Cl₂, cyclopentene-yne 14a gave 5,7-fused

Table 2. ROM-RCM of cycloalkene-yne 14a

Run

Time (h)

Yield (%)

1

2

26

4

96

2

Quant.

90

81

3^a

4^b

1

a

5 mol % of 1b was used.

Reactions were carried out under an atmosphere of Ar.

b

Furthermore, ROM-RCM of cycloheptene-yne 14c was

investigated (Table 3). When the reaction of 14c was carried

out in toluene at 80 8C for 21 h, 5,7-fused ring compound

17a, dimeric compound 18c and isoindoline derivative 21¹⁵

were obtained in 36, 8 and 6% yields, respectively, along

with an inseparable mixture of 22 (run 1). GC–MS analysis

of 22 showed that it is a mixture of dihydropyrrole

derivatives having different carbon lengths and/or having

oleﬁn at various positions in a tether. On the other hand,

when the reaction was carried out in CH₂Cl₂upon heating

Scheme 16. Summary of ROM-RCM of cycloalkene-yne 14a–14c.

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

7381

ring compound 17a in high yield, but cycloheptene-yne 14c

afforded dimeric compound 18c in high yield. However,

under similar reaction conditions, cyclohexene-yne 14b

gave 17a and dimeric compound 18b in 26 and 57% yields,

respectively. Since the reaction of 14c in toluene at 80 8C

gave 17a in good yield, 17a was obtained in all cases due to

the easy isomerization of the terminal oleﬁn in a tether and

the easy formation of a seven-membered ring.

Furthermore, ROM-RCM of cycloalkenecarboxamide

having an alkyne moiety on nitrogen was carried out.

When a toluene solution of 14d and 10 mol% of 1b was

stirred in toluene at 80 8C for 1 h under an atmosphere of

ethylene, the desired 5,7-fused ring compound 17d was

obtained in 66% yield as a single product. On the other

hand, when ROM-RCM of cyclohexene-yne 14e was

carried out in a similar manner, 5,8-fused ring compound

17e, dimeric compound 18e, pyrrolidine derivative 19d and

cross-metathesis product 23 with ethylene were obtained in

24, 17, 13 and 17% yields, respectively. In this case, it was

interesting that 5,7-fused ring compound 17d was not

formed. Presumably, before isomerization of the double

bond of 19d, oleﬁn metathesis should occur to give 17e,

which is stable under the reaction conditions. Although it is

not clear why a dimeric compound is formed, a relatively

large amount of dimeric compound 18e was also obtained in

this case. Since compound 19d was thought to be a product

of ring-opening metathesis followed by cross-metathesis

with ethylene, further treatment of compound 19d with 1b

was carried out. When a CH₂Cl₂solution of 19d and

10 mol% of 1b was reﬂuxed for 1.5 h under argon gas

upon heating, 5,8-fused ring compound 17e and dimeric

Scheme 18. Reaction of 19d with 1b.

compound 18e were obtained in 51 and 40% yields,

respectively (Scheme 17 and 18).

3. Conclusions

ROM-RCM of cycloalkene-yne was realized. In the ﬁrst

ROM-RCM of cycloalkene having alkyne in a tether at the

C-3 position, the reaction proceeded smoothly and the

expected products were obtained in high yields. Ethylene

gas is essential for these reactions. Formally, in this

reaction, the double bond of cycloalkene was cleaved, and

one alkylidene carbon reacts with an alkyne carbon to form

a ﬁve-membered ring, while the other alkylidene carbon and

alkyne carbon react with methylene parts of ethylene to

form two terminal oleﬁns, respectively. However, in the

second ROM-RCM of cycloalkene having alkyne in a tether

at the C-1 position, unexpected 5,7-fused ring compound

17a was formed from all cycloalkene-ynes. Moreover,

dimeric compounds 18 were obtained from cyclohexene and

cycloheptene derivatives. Presumably, the reaction rate of

ROM-RCM of cyclopentene is fast and the expected stable

product 17a would be produced predominantly. However,

since ROM-RCM products of cyclohexene and cyclo-

heptene derivatives were unstable under these reaction

conditions, further reactions would proceed to give a

dimeric compound and the cross-metathesis product with

ethylene.

4. Experimental

4.1. General

The metathesis reactions were carried out under an

atmosphere of ethylene (1 atm). All other manipulations

were carried out under an atmosphere of argon unless

otherwise mentioned. Solvents were distilled under an

atmosphere of argon from sodium–benzophenone (tolu-

ene), or CaH₂(CH₂Cl₂). Ethylene gas was puriﬁed by

passage through the aqueous CuCl solution (2 g of CuCl in

180 mL of saturated NH₄Cl aqueous) and concentrated

H₂SO₄and then KOH tubes. Ruthenium complexes were

purchased from Strem Chemicals. All other solvents and

reagents were puriﬁed when necessary using standard

procedure.

Scheme 17. ROM-RCM of cycloalkene-yne 14d and 14e.

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T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

4.2. Typical procedure for the metathesis reaction

d 1.24–1.49 (m, 2H), 1.76–1.85 (m, 2H), 2.06 (dt, J¼6.8,

7.3 Hz, 2H), 2.41 (s, 3H), 4.16–4.28 (m, 2H), 4.50 (br, 1H),

4.92–5.03 (m, 2H), 5.01 (d, J¼17.8 Hz, 1H), 5.14 (d,

J¼10.5 Hz, 1H), 5.51 (br, 1H), 5.78 (ddt, J¼17.0, 10.3,

6.8 Hz, 1H), 6.32 (dd, J¼17.8, 10.5 Hz, 1H), 7.29 (d, J¼

8.1 Hz, 2H), 7.71 (d, J¼8.3 Hz, 2H); ¹³C NMR (67.8 MHz,

CDCl₃) d 21.5 (CH₃), 23.9 (CH₂), 33.7 (CH₂), 35.5 (CH₂),

54.3 (CH₂), 67.3 (CH), 114.6 (CH₂), 116.7 (CH₂), 127.3

(CH£2), 127.8 (CH), 129.7 (CH£2), 129.9 (CH), 134.8 (C),

136.6 (C), 138.5 (CH), 143.3 (C); LRMS m/z 317 (M^þ),

248, 155, 91; HRMS calcd for C₁₈H₂₃NO₂S (M^þ) 317.1449,

found 317.1455.

To a solution of enyne 2d (98.2 mg, 0.34 mmol) in a CH₂Cl₂

solution (11.3 mL) was added 1a (26.1 mg, 34 mmol), and

the solution was degassed through freeze–pump–thaw

cycle, and stirred at room temperature under an atmosphere

of ethylene for 4 h. To this solution was added an excess of

ethyl vinyl ether. After the solvent was removed, the residue

was puriﬁed by ﬂash column chromatography on silica gel

(hexane/ethyl acetate 9:1) to yield 4d (83.6 mg, 78%) as a

colorless solid.

4.3. Spectral data for metathesis products

4.3.5. 2-Hex-5-enyl-1-(toluene-4-sulfonyl)-4-vinyl-2,5-

dihydro-1H-pyrrole (4e). A colorless oil; IR (neat) n

1640, 1598, 1346, 1162 cm²¹; ¹H NMR (270 MHz, CDCl₃)

d 1.23–1.46 (m, 4H), 1.71–1.86 (m, 2H), 2.04 (dt, J¼6.7,

6.5 Hz, 2H), 2.41 (s, 3H), 4.16–4.28 (m, 2H), 4.49 (br, 1H),

4.91–5.03 (m, 2H), 5.01 (d, J¼17.8 Hz, 1H), 5.14 (d, J¼

11.1 Hz, 1H), 5.52 (m, 1H), 5.79 (ddt, J¼17.0, 10.1, 6.7 Hz,

1H), 6.33 (dd, J¼17.8, 11.1 Hz, 1H), 7.29 (d, J¼8.1 Hz,

2H), 7.71 (d, J¼8.1 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃)

d 21.4 (CH₃), 24.1 (CH₂), 28.8 (CH₂), 33.6 (CH₂), 35.9

(CH₂), 54.2 (CH₂), 67.4 (CH), 114.3 (CH₂), 116.6 (CH₂),

127.3 (CH£2), 127.9 (CH), 129.7 (CH£2), 129.9 (CH),

134.5 (C), 136.6 (C), 138.8 (CH), 143.3 (C); LRMS m/z 331

(M^þ), 248, 155, 91; HRMS calcd for C₁₉H₂₅NO₂S (M^þ)

331.1606, found 331.1604.

4.3.1. 4-Isopropenyl-2-pent-4-enyl-1-(toluene-4-sulfonyl)-

2,5-dihydro-1H-pyrrole (4a). A colorless oil; IR (neat) n

1640, 1600, 1346, 1164 cm²¹; ¹H NMR (270 MHz, CDCl₃)

d 1.31–1.52 (m, 2H), 1.77–1.86 (m, 2H), 1.83 (s, 3H), 2.07

(dt, J¼6.7, 7.3 Hz, 2H), 2.41 (s, 3H), 4.19–4.27 (m, 2H),

4.52 (br, 1H), 4.76 (s, 1H), 4.93–5.04 (m, 3H), 5.50 (s, 1H),

5.79 (ddt, J¼17.0, 10.1, 6.7 Hz, 1H), 7.29 (d, J¼8.3 Hz,

2H), 7.71 (d, J¼8.3 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃)

d 20.0 (CH₃), 21.5 (CH₃), 24.0 (CH₂), 33.7 (CH₂), 35.6

(CH₂), 55.2 (CH₂), 67.8 (CH), 114.5 (CH₂), 114.7 (CH₂),

125.0 (CH), 127.4 (CH£2), 129.7 (CH£2), 134.9 (C), 136.6

(C), 138.4 (C), 138.6 (CH), 143.3 (C); LRMS m/z 331 (M^þ),

262, 176, 155, 107, 91; HRMS calcd for C₁₉H₂₅NO₂S (M^þ)

331.1606, found 331.1613.

4.3.2. 2-Hex-5-enyl-4-isopropenyl-1-(toluene-4-sulfo-

nyl)-2,5-dihydro-1H-pyrrole (4b). A colorless oil; IR

4.3.6. 2-Hept-6-enyl-1-(toluene-4-sulfonyl)-4-vinyl-2,5-

dihydro-1H-pyrrole (4f). A colorless oil; IR (neat) n

1640, 1598, 1346, 1164 cm²¹; ¹H NMR (270 MHz, CDCl₃)

d 1.21–1.39 (m, 6H), 1.73–1.82 (m, 2H), 1.99–2.06 (m,

2H), 2.41 (s, 3H), 4.16–4.29 (m, 2H), 4.49 (br, 1H), 4.90–

5.03 (m, 2H), 5.01 (d, J¼17.6 Hz, 1H), 5.14 (d, J¼10.8 Hz,

1H), 5.52 (m, 1H), 5.80 (ddt, J¼17.0, 10.3, 6.8 Hz, 1H),

6.33 (dd, J¼17.6, 10.8 Hz, 1H), 7.29 (d, J¼8.1 Hz, 2H),

7.71 (d, J¼8.1 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d

21.5 (CH₃), 24.4 (CH₂), 28.8 (CH₂), 29.0 (CH₂), 33.7 (CH₂),

36.0 (CH₂), 54.3 (CH₂), 67.5 (CH), 114.2 (CH₂), 116.6

(CH₂), 127.3 (CH£2), 127.9 (CH), 129.7 (CH£2), 123.0

(CH), 134.9 (C), 136.6 (C), 139.0 (CH), 143.3 (C); LRMS

m/z 345 (M^þ), 248, 155, 106, 91; HRMS calcd for

C₂₀H₂₇NO₂S (M^þ) 345.1762, found 345.1760.

(neat) n1640, 1600, 1346, 1164 cm²¹

;

¹H NMR

(270 MHz, CDCl₃) d 1.26–1.43 (m, 4H), 1.75–1.87 (m,

2H), 1.83 (s, 3H), 2.04 (dt, J¼6.5, 6.5 Hz, 2H), 2.41 (s, 3H),

4.19–4.31 (m, 2H), 4.51 (br, 1H), 4.76 (s, 1H), 4.92 (m,

1H), 4.96 (m, 1H), 5.02 (m, 1H), 5.50 (s, 1H), 5.80 (ddt,

J¼17.0, 10.1, 6.7 Hz, 1H), 7.29 (d, J¼8.1 Hz, 2H), 7.71 (d,

J¼8.1 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d 20.0 (CH₃),

21.5 (CH₃), 24.1 (CH₂), 28.9 (CH₂), 33.6 (CH₂), 35.9 (CH₂),

55.2 (CH₂), 67.8 (CH), 114.3 (CH₂), 114.5 (CH₂), 125.1

(CH), 127.4 (CH£2), 129.7 (CH£2), 134.9 (C), 136.6 (C),

138.3 (C), 138.8 (CH), 143.3 (C); LRMS m/z 345 (M^þ),

262, 155, 107, 91; HRMS calcd for C₂₀H₂₇NO₂S (M^þ)

345.1762, found 345.1752.

4.3.3. 2-Hept-6-enyl-4-isopropenyl-1-(toluene-4-sulfo-

nyl)-2,5-dihydro-1H-pyrrole (4c). A colorless oil; IR

(neat)

4.3.7. N-{(1R ^p,4S ^p)-4-(tert-Butyl-dimethylsilanyloxy)-

cyclohex-2-enyl}-4-methyl-N-(2-methylene-but-3-enyl)-

benzenesulfonamide (8a). A colorless oil; IR (neat) n 1638,

n ;

1640, 1598, 1346, 1164 cm^{21 1}H NMR

1

(400 MHz, CDCl₃) d 1.24–1.86 (m, 8H), 1.82 (s, 3H), 2.03

(dt, J¼6.7, 6.4 Hz, 2H), 2.41 (s, 3H), 4.20–4.30 (m, 2H), 4.50

(br, 1H), 4.76 (s, 1H), 4.92–5.01 (m, 2H), 4.96 (s, 1H), 5.50

(s, 1H), 5.80 (ddt, J¼16.7, 10.0, 6.7 Hz, 1H), 7.29 (d, J¼

8.3 Hz, 2H), 7.71 (d, J¼8.3 Hz, 2H); ¹³C NMR (100 MHz,

CDCl₃) d 20.1 (CH₃), 21.6 (CH₃), 24.5 (CH₂), 28.9 (CH₂),

29.2 (CH₂), 33.8 (CH₂), 36.1 (CH₂), 55.2 (CH₂), 67.9 (CH),

114.2 (CH₂), 114.4 (CH₂), 125.1 (CH), 127.3 (CH£2), 129.6

(CH£2), 134.8 (C), 136.5 (C), 138.1 (C), 138.9 (CH), 143.2

(C); LRMS m/z 359 (M^þ), 262, 155, 107, 91; HRMS calcd

for C₂₁H₂₉NO₂S (M^þ) 359.1919, found 359.1919.

1598, 1342, 1253, 1163, 1093 cm²¹; H NMR (270 MHz,

CDCl₃) d 20.02 (s, 3H), 20.01 (s, 3H), 0.81 (s, 9H), 1.54–

1.66 (m, 3H), 1.79–1.87 (m, 1H), 2.43 (s, 3H), 3.76

(d, J¼17.6 Hz, 1H), 4.00 (br, 1H), 4.04 (d, J¼17.6 Hz,

1H), 4.44–4.48 (m, 1H), 5.03–5.09 (m, 2H), 5.17–5.24

(m, 2H), 5.42 (br, 1H), 5.69–5.75 (m, 1H), 6.40 (dd,

J¼18.1, 11.3 Hz, 1H), 7.30 (d, J¼8.4 Hz, 2H), 7.74 (d,

J¼8.4 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d 24.9

(CH₃), 24.6 (CH₃), 17.9 (C), 21.5 (CH₃), 22.9 (CH₂),

25.7 (CH₃£3), 30.4 (CH₂), 45.1 (CH₂), 55.6 (CH), 62.6

(CH), 113.3 (CH₂), 117.4 (CH₂), 127.2 (CH£2), 129.0

(CH), 129.7 (CH£2), 134.1 (CH), 136.9 (CH), 137.9 (C),

142.5 (C), 143.2 (C); LRMS m/z 447 (M^þ), 390, 248, 132,

91; HRMS calcd for C₂₄H₃₇NO₃SSi (M^þ) 447.2263, found

447.2244.

4.3.4. 2-Pent-4-enyl-1-(toluene-4-sulfonyl)-4-vinyl-2,5-

dihydro-1H-pyrrole (4d). A colorless solid; IR (nujol) n

1642, 1598, 1344, 1166 cm²¹; ¹H NMR (270 MHz, CDCl₃)

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

7383

4.3.8. (2S ^p)-2-{(3S ^p)-3-(tert-Butyl-dimethylsilanyloxy)-

pent-4-enyl}-1-(toluene-sulfonyl)-4-vinyl-2,5-dihydro-

1H-pyrrole (9b). A colorless oil; IR (neat) n 1646, 1598,

1348, 1252, 1163, 1096 cm²¹; ¹H NMR (400 MHz, CDCl₃)

d 0.03 (s, 3H), 0.06 (s, 3H), 0.89 (s, 9H), 1.41–1.57 (m, 2H),

1.76–1.91 (m, 2H), 2.41 (s, 3H), 4.07 (dt, J¼6.4, 6.0 Hz,

1H), 4.17–4.26 (m, 2H), 4.54 (br, 1H), 4.98 (d, J¼17.6 Hz,

1H), 5.01 (d, J¼10.4 Hz, 1H), 5.13 (d, J¼17.2 Hz, 1H),

5.14 (d, J¼10.8 Hz, 1H), 5.47 (br, 1H), 5.76 (ddd, J¼17.2,

10.4, 6.4 Hz, 1H), 6.32 (dd, J¼17.6, 10.8 Hz, 1H), 7.29

(d, J¼8.4 Hz, 2H), 7.71 (d, J¼8.4 Hz, 2H); ¹³C NMR

(100 MHz, CDCl₃) d 24.7 (CH₃), 24.2 (CH₃), 18.3 (C),

21.6 (CH₃), 25.9 (CH₃£3), 31.7 (CH₂), 32.7 (CH₂), 54.4

(CH₂), 67.3 (CH), 73.7 (CH), 113.7 (CH₂), 116.6 (CH₂),

127.3 (CH£2), 127.7 (CH), 129.6 (CH£2), 129.8 (CH),

134.7 (C), 136.6 (C), 141.5 (CH), 143.3 (C); LRMS m/z

432 (M^þ2CH₃), 390, 292, 262, 248, 236, 155, 91; HRMS

calcd for C₂₃H₃₄NO₃SSi (M^þ2CH₃) 432.2067, found

432.2048. Anal. calcd for C₂₄H₃₇NO₃SSi: C, 64.39; H,

8.33; N, 3.13; S, 7.16. Found: C, 64.48; H, 8.48; N, 2.91; S,

7.21.

4.3.11. N-Cyclohex-2-enyl-4-methyl-N-(3-methylene-

pent-4-enyl)-benzenesulfonamide (12h). A colorless oil;

IR (neat) n 2934, 1648, 1595, 1494, 1450, 1392, 1340, 1224,

1160, 1126, 1097, 1019 cm²¹; ¹H NMR (270 MHz, CDCl₃)

d 1.48–1.96 (m, 6H), 2.42 (s, 3H), 2.46–2.82 (m, 2H),

2.99–3.28 (m, 2H), 4.48 (m, 1H), 5.01 (s, 1H), 5.05 (s, 1H),

5.07–5.12 (m, 1H), 5.11 (d, J¼10.8 Hz, 1H), 5.40 (d, J¼

17.3 Hz, 1H), 5.75–5.80 (m, 1H), 6.33 (dd, J¼10.8,

17.3 Hz, 1H), 7.28 (d, J¼8.1 Hz, 2H), 7.72 (d, J¼8.1 Hz,

2H); ¹³C NMR (67.8 MHz, CDCl₃) d 21.5 (CH₃), 21.8

(CH₂), 24.4 (CH₂), 29.0 (CH₂), 34.6 (CH₂), 44.0 (CH₂),

55.4 (CH), 114.2 (CH₂), 117.3 (CH₂), 127.1 (CH), 127.7

(CH£2), 129.7 (CH£2), 132.3 (CH), 138.1 (C), 138.2 (CH),

143.0 (C), 145.9 (C); LRMS m/z 331 (M^þ), 316, 288, 364,

351, 184, 176, 155, 91; HRMS calcd for C₁₉H₂₅NO₂S (M^þ)

331.1606, found 331.1605.

4.3.12. N-Cyclohex-1-enylmethyl-4-methyl-N-(2-methyl-

ene-but-3-enyl)-benzenesulfonamide (15b). A colorless

oil; IR (neat) n 1597, 1338, 1160 cm²¹

;

¹H NMR

(400 MHz, CDCl₃d 1.46–1.51 (m, 4H), 1.81 (br, 2H),

1.90 (br, 2H), 2.42 (s, 3H), 3.64 (s, 2H), 3.91 (s, 2H), 5.05 (s,

1H), 5.06 (d, J¼10.8 Hz, 1H), 5.13 (s, 1H), 5.29 (d, J¼

18.0 Hz, 1H), 5.46 (br, 1H), 6.30 (dd, J¼18.0, 10.8 Hz, 1H),

7.29 (d, J¼8.4 Hz, 2H), 7.70 (d, J¼8.4 Hz, 2H); ¹³C NMR

(100 MHz, CDCl₃) d 21.5 (CH₃), 22.1 (CH₂), 22.5 (CH₂),

25.2 (CH₂), 26.2 (CH₂), 48.6 (CH₂), 54.6 (CH₂), 114.3

(CH₂), 117.6 (CH₂), 126.8 (CH), 127.2 (CH£2), 129.4

(CH£2), 132.3 (C), 136.6 (CH), 137.0 (C), 140.3 (C), 142.9

(C); LRMS m/z 331 (M^þ), 316, 302, 290, 276, 264, 249,

236, 198, 184, 176, 155, 148, 133, 119, 106; HRMS calcd

for C₁₉H₂₅NO₂S (M^þ) 331.1606, found 331.1606. Anal.

calcd for C₁₉H₂₅NO₂S: C, 68.85; H, 7.60; N, 4.23; S, 9.67.

Found: C, 68.73; H, 7.61; N, 4.29; S, 9.77.

4.3.9. (2S ^p)-2-[(2R ^p)-2-(tert-Butyl-dimethyl-silanyloxy)-

but-3-enyl]-1-(toluene-4-sulfonyl)-4-vinyl-2,5-dihydro-

1H-pyrrole (9c). A colorless oil; IR (neat) n 2954, 2928,

1

2856, 1646, 1599, 1348, 1163 cm²¹; H NMR (270 MHz,

CDCl₃) d 0.00 (s, 3H), 0.02 (s, 3H), 0.88 (s, 9H), 1.75 (ddd,

J¼13.8, 9.7, 4.3 Hz, 1H), 2.37 (m, 1H), 2.39 (s, 3H), 4.12

(m, 1H), 4.22 (m, 1H), 4.28 (m, 1H), 4.48 (br, 1H), 4.98 (d,

J¼17.6 Hz, 1H), 5.09 (dt, J¼10.8 1.6 Hz, 1H), 5.11 (d,

J¼10.3 Hz, 1H), 5.20 (dt, J¼17.8, 1.6 Hz,1H), 5.68 (br,

1H), 5.88 (ddd, J¼17.6, 10.3, 5.7 Hz, 1H), 6.29 (dd, J¼17.8,

10.8 Hz, 1H), 7.26 (d, J¼9.7 Hz, 2H), 7.68 (d, J¼9.7 Hz,

2H); ¹³C NMR (67.8 MHz, CDCl₃) d 25.0 (CH₃), 24.3

(CH₃), 18.1 (C), 21.5 (CH₃), 25.8 (CH₃£3), 44.5 (CH₂),

53.9 (CH₂), 64.4 (CH), 71.2 (CH), 114.3 (CH₂), 116.5

(CH₂), 127.5 (CH£2), 128.8 (CH), 129.7 (CH£2), 130.1

(CH), 134.2 (C), 135.6 (C), 140.8 (CH), 143.4 (C); LRMS

m/z 432 (M^þ21), 418, 403, 376, 278, 220, 155, 91. Anal.

calcd for C₂₃H₃₅NO₃SSi: C, 63.70; H, 8.13; N, 3.23; S, 7.39.

Found: C, 63.47; H, 8.07; N, 3.20; S, 7.23.

4.3.13. 2-(Toluene-4-sulfonyl)-1,2,3,4,5,6-hexahydro-

cyclohepta[c]pyrrole (17a). A colorless crystals. Mp

111–113 8C (ether); IR (nujol) n 2924, 2854, 1654, 1344,

1

1163 cm²¹; H NMR (400 MHz, CDCl₃) d 1.78 (m, 2H),

2.20 (br, 2H), 2.31 (m, 2H), 2.43 (s, 3H), 4.10 (br, 4H), 5.52

(d, J¼11.6 Hz, 1H), 5.83 (dt, J¼11.6, 5.6 Hz, 1H), 7.32

(d, J¼8.0 Hz, 2H), 7.72 (d, J¼8.0 Hz, 2H); ¹³C NMR

(100 MHz, CDCl₃) d 21.6 (CH₃), 23.4 (CH₂), 29.5 (CH₂),

30.6 (CH₂), 58.4 (CH₂), 59.5 (CH₂), 120.3 (CH), 127.2 (C),

127.4 (CH£2), 129.6 (CH£2), 133.9 (C), 134.1 (C), 134.7

(CH), 143.2 (C); LRMS m/z 289 (M^þ), 155, 134, 91; HRMS

calcd for C₁₆H₁₉NO₂S (M^þ) 289.1136, found 289.1124.

4.3.10. (2S ^p)-2-[(2S ^p)-2-(tert-Butyl-dimethyl-silanyl-

oxy)-but-3-enyl]-1-(toluene-4-sulfonyl)-4-vinyl-2,5-di-

hydro-1H-pyrrole (9d). A colorless solid. Mp 91 8C (ether/

hexane); IR (nujol) n 3088, 1829, 1597, 1343, 1165 cm²¹

;

¹H NMR (270 MHz, CDCl₃) d 0.04 (s, 3H), 0.08 (s, 3H),

0.89 (s, 9H), 1.77–1.85 (m, 1H), 2.25–2.31 (m, 1H), 2.39

(s, 3H), 4.02 (m, 1H), 4.10 (m, 1H), 4.30–4.35 (m, 1H), 4.46

(br, 1H), 4.97 (d, J¼17.8 Hz, 1H), 5.05 (dt, J¼10.4, 1.6 Hz,

1H), 5.10 (d, J¼10.4 Hz, 1H), 5.16 (dt, J¼17.8, 1.6 Hz,1H),

5.63 (br, 1H), 5.79 (ddd, J¼17.8, 10.4, 6.2 Hz, 1H), 6.28

(dd, J¼17.8, 10.4 Hz, 1H), 7.27 (d, J¼8.2 Hz, 2H), 7.68

(d, J¼8.2 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d 24.7

(CH₃), 24.3 (CH₃), 18.2 (C), 21.5 (CH₃), 25.9 (CH₃£3),

45.0 (CH₂), 53.7 (CH₂), 65.2 (CH), 72.0 (CH), 114.3 (CH₂),

116.5 (CH₂), 127.5 (CH£2), 128.8 (CH), 129.7 (CH£2),

130.1 (CH), 134.2 (C), 135.6 (C), 147.4 (CH), 143.4 (C);

LRMS m/z 433 (M^þ), 418, 376, 278, 248, 220, 155, 91;

HRMS calcd for C₂₂H₃₂NO₃SSi (M^þ2Me) 418.1892,

found 418.1872. Anal. calcd for C₂₃H₃₅NO₃SSi: C, 63.70;

H, 8.13; N, 3.23; S, 7.39. Found: C, 63.68; H, 8.12; N, 3.20;

S, 7.29.

4.3.14. Dimeric compound 18b. A colorless solid; IR

1

(nujol) n 2924, 2854, 1598, 1348, 1157 cm²¹; H NMR

(400 MHz, CDCl₃) d 1.29–1.39 (m, 8H), 2.05–2.09 (m,

4H), 2.12–2.16 (m, 4H), 2.41 (s, 6H), 4.06 (s, 4H), 4.16 (s,

4H), 5.34 (m, 2H), 6.10 (d, J¼16.0 Hz, 2H), 7.30 (d, J¼

8.0 Hz, 4H), 7.70 (d, J¼8.0 Hz, 4H); ¹³C NMR (100 MHz,

CDCl₃) d 21.5 (CH₃£2), 24.4 (CH₂£2), 25.6 (CH₂£2), 26.8

(CH₂£2), 30.9 (CH₂£2), 55.1 (CH₂£2), 57.5 (CH₂£2),

121.8 (CH£2), 127.4 (CH£4), 129.0 (C£2), 129.7 (CH£4),

131.6 (CH£2), 133.2 (C£2), 134.3 (C£2), 143.4 (C£2);

LRMS m/z 606 (M^þ), 518, 451, 295, 155, 91; HRMS calcd

for C₃₄H₄₂N₂O₄S₂(M^þ) 606.2586, found 606.2581.

4.3.15. 2-(Toluene-4-sulfonyl)-2,3,4,5,6,7-hexahydro-1H-

cycloocta[c]pyrrole (17b). A colorless solid; IR (nujol) n

7384

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

1

2924, 2854, 1654, 1344, 1162 cm²¹; H NMR (270 MHz,

CDCl₃) d 1.45–1.52 (m, 2H), 1.59–1.67 (m, 2H), 2.03–

2.07 (m, 2H), 2.13–2.17 (m, 2H), 2.43 (s, 3H), 4.03 (s, 4H),

5.62–5.66 (m, 2H), 7.32 (d, J¼8.1 Hz, 2H), 7.72 (d,

J¼8.1 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d 21.6 (CH₃),

21.6 (CH₂), 25.4 (CH₂), 27.0 (CH₂), 27.1 (CH₂), 58.2 (CH₂),

59.2 (CH₂), 122.3 (CH), 127.1 (C), 127.5 (CH£2), 129.7

(CH£2), 132.7 (CH), 132.9 (C), 134.3 (C), 143.3 (C);

LRMS m/z 303 (M^þ), 155, 148, 91; HRMS calcd for

C₁₇H₂₁NO₂S (M^þ) 303.1293, found 303.1299.

4.3.20. Dimeric compound 18e. A colorless liquid; IR

1

(neat) n 1678 (s), 1480 (m), 1453 (m), 1410 (m) cm²¹; H

NMR (270 MHz, CDCl₃) d 1.46–1.64 (m, 8H), 2.20–2.29

(m, 4H), 2.36–2.43 (m, 4H), 3.83 (br, 4H), 4.61 (br, 4H),

5.80 (dt, J¼6.6, 16.0 Hz, 2H), 6.42 (d, J¼16.0 Hz, 2H),

7.21–7.34 (m, 10H); EI-LRMS m/z 506 (M^þ), 415, 368,

304, 227, 91; EI-HRMS m/z calcd for C₃₄H₃₈O₂N₂(M^þ)

506.2933, found 506.2916.

4.3.21. N-Benzyl-3-(hex-5-enyl)-4-vinyl-5-hydro-1H-

pyrrol-1-one (19d). A colorless liquid; IR (neat) n 1681

1

4.3.16. 3-Hex-5-enyl-1-(toluene-4-sulfonyl)-4-vinyl-2,5-

dihydro-1H-pyrrole (19b). A colorless solid; IR (ﬁlm) n

;

2926, 2855, 1654, 1598, 1347, 1164 cm^{21 1}H NMR

(s), 1640 (m), 1624 (m), 1452 (m), 1408 (m) cm²¹; H

NMR (270 MHz, CDCl₃) d 1.40–1.64 (m, 4H), 2.03–2.13

(m, 2H), 2.40 (t, J¼7.4 Hz, 2H), 3.87 (s, 2H), 4.64 (s, 2H),

4.90–5.04 (m, 2H), 5.28 (d, J¼10.9 Hz, 1H), 5.31 (d, J¼

17.6 Hz, 1H), 5.81 (ddt, J¼10.2, 17.0, 6.6 Hz, 1H), 6.70 (dd,

J¼10.9, 17.6 Hz, 1H), 7.21–7.38 (m, 5H); EI-LRMS m/z

281 (M^þ), 252, 240, 226, 213, 190, 149, 122, 109, 91;

EI-HRMS m/z calcd for C₁₉H₂₃ON (M^þ) 281.1779, found

281.1755.

(400 MHz, CDCl₃) d 1.26–1.40 (m, 4H), 1.98–2.05 (m,

2H), 2.12–2.15 (m, 2H), 2.43 (s, 3H), 4.11 (s, 2H), 4.22 (s,

2H), 4.93–4.99 (m, 3H), 5.12 (d, J¼10.8 Hz, 1H), 5.74 (m,

1H), 6.43 (dd, J¼17.2, 10.8 Hz, 1H), 7.32 (d, J¼8.1 Hz,

2H), 7.73 (d, J¼8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃)

d 21.6 (CH₃), 26.0 (CH₂), 27.3 (CH₂), 28.5 (CH₂), 33.4

(CH₂), 54.9 (CH₂), 57.6 (CH₂), 114.7 (CH₂), 115.3 (CH₂),

127.4 (CH£2), 129.4 (CH), 129.7 (CH£2), 130.8 (C), 133.9

(C), 135.8 (C), 138.3 (CH), 143.4 (C); LRMS m/z 331 (M^þ),

248, 176, 155, 91; HRMS calcd for C₁₉H₂₅NO₂S (M^þ)

331.1606, found 331.1592.

4.3.22. N-Benzyl-N-(2-methylene-but-3-enyl)-1-cyclo-

hexene-1-carboxamide (23). A colorless liquid; IR (neat)

n 1658 (m), 1621 (s), 1495 (m), 1453 (s), 1418 (s) cm²¹; ¹H

NMR (270 MHz, CDCl₃) d 1.55–1.72 (m, 4H), 2.02–2.10

(m, 2H), 2.21–2.27 (m, 2H), 4.02–4.22 (m, 2H), 4.58 (s,

2H), 4.88–5.36 (m, 4H), 5.87 (m, 1H), 6.38 (dd, J¼11.0,

17.7 Hz, 1H), 7.15–7.38 (m, 5H); EI-LRMS m/z 281 (M^þ),

240, 214, 190, 172, 109; EI-HRMS m/z calcd for C₁₉H₂₃ON

(M^þ) 281.1779, found 281.1754.

4.3.17. Dimeric compound 18c. A colorless solid; IR

1

(nujol) n 2923, 2854, 1598, 1348, 1157 cm²¹; H NMR

(400 MHz, CDCl₃) d 0.99–1.38 (m, 12H), 2.01–2.14 (m,

8H), 2.42 (s, 6H), 4.05 (s, 4H), 4.19 (s, 4H), 5.33 (m, 2H),

6.02 (d, J¼15.6 Hz, 2H), 7.32 (d, J¼8.0 Hz, 4H), 7.73 (d,

J¼8.0 Hz, 4H); ¹³C NMR (100 MHz, CDCl₃) d 21.6

(CH₃£2), 25.3 (CH₂£2), 26.9 (CH₂£2), 27.0 (CH₂£2),

27.9 (CH₂£2), 33.1 (CH₂£2), 55.2 (CH₂£2), 57.0 (CH₂£2),

121.6 (CH£2), 127.4 (CH£4), 129.5 (C£2), 129.6

(CH£4), 132.1 (CH£2), 132.4 (C£2), 134.1 (CH£2),

143.3 (C£2); LRMS m/z 634 (M^þ), 479. 451, 323, 155,

91; HRMS calcd for C₃₆H₄₆N₂O₄S₂(M^þ) 634.2899, found

634.2902.

4.4. Procedure for the Diels–Alder reaction

4.4.1. (2S ^p)-2-{(3S ^p)-3-Hydroxy-pent-4-enyl}-1-(toluene-

sulfonyl)-4-vinyl-2,5-dihydro-1H-pyrrole. A solution of

9b (55 mg, 0.12 mmol) in THF (1.0 mL) was added TBAF

(1.0 M in THF, 0.2 mL, 0.2 mmol) at 0 8C, and the solution

was stirred at room temperature for 3 h. To this solution was

added saturated NH₄Cl aq., and the aqueous layer was

extracted with ethyl acetate. The organic layer was washed

with brine, dried over Na₂SO₄, and evaporated. The residue

was puriﬁed by column chromatography on silica gel

(hexane/ethyl acetate 4:1–1:1) to yield title alcohol (40 mg,

98%) as a colorless oil. IR (neat) n 3518, 1647, 1598, 1342,

4.3.18. N-Benzyl-3,6,7,8-tetrahydro-cyclohepta[c]-

pyrrol-1(2H)-one (17d). A colorless liquid; IR (neat) n

1

1674 (s), 1495 (m), 1452 (s) cm²¹; H NMR (270 MHz,

CDCl₃) d 1.84–1.92 (m, 2H), 2.47 (dt, J¼5.6, 5.4 Hz, 2H),

2.63 (br, 2H), 3.71 (t, J¼2.2 Hz, 2H), 4.63 (s, 2H), 5.78 (dt,

J¼11.3, 2.0 Hz, 1H), 6.10 (dt, J¼11.3, 5.6 Hz, 1H), 7.23–

7.35 (m, 5H); ¹³C NMR (67.8 MHz, CDCl₃) d 22.8, 27.3,

31.9, 46.2, 52.4, 121.0, 127.3, 127.9, 128.6, 133.9, 137.4,

139.1, 143.8, 172.0; EI-LRMS m/z 239 (M^þ), 162, 148, 105,

91, 77; EI-HRMS m/z calcd for C₁₆H₁₇ON (M^þ) 239.1310,

found 239.1320.

1

1160 cm²¹; H NMR (400 MHz, CDCl₃) d 1.45–1.53 (m,

1H), 1.59–1.68 (m, 1H), 1.86 (br, 1H), 1.87–1.92 (m, 2H),

2.41 (s, 3H), 4.13 (dt, J¼6.4, 6.4 Hz, 1H), 4.17–4.28 (m,

2H), 4.57 (m, 1H), 5.01 (d, J¼17.6 Hz, 1H), 5.11 (d, J¼

10.0 Hz, 1H), 5.11 (d, J¼10.8 Hz, 1H), 5.23 (d, J¼17.6 Hz,

1H), 5.48 (m, 1H), 5.85 (ddd, J¼17.6, 10.0, 6.4 Hz, 1H),

6.32 (dd, J¼17.6, 10.8 Hz, 1H), 7.30 (d, J¼8.0 Hz, 2H),

7.71 (d, J¼8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃) d

21.5 (CH₃), 31.5 (CH₂), 31.5 (CH₂), 54.4 (CH₂), 67.0 (CH),

72.9 (CH), 114.7 (CH₂), 116.8 (CH₂), 127.3 (CH£2), 127.5

(CH), 129.6 (CH£2), 129.7 (CH), 134.3 (C), 136.6 (C),

140.8 (CH), 143.4 (C); LRMS m/z 315 (M^þ2H₂O), 248,

178, 155, 91; HRMS calcd for C₁₈H₂₁NO₂S (M^þ2H₂O)

315.1293, found 315.1301.

4.3.19. N-Benzyl-2,3,6,7,8,9-hexahydro-1H-cycloocta[c]-

pyrrol-1-one (17e). A colorless liquid; IR (neat) n 1683 (s),

1636 (m), 1604 (w), 1495 (m), 1453 (s) cm²¹; H NMR

1

(270 MHz, CDCl₃) d 1.55–1.64 (m, 2H), 1.78–1.87 (m,

2H), 2.27–2.34 (m, 2H), 2.48–2.52 (m, 2H), 3.64 (t,

J¼2.1 Hz, 2H), 4.62 (s, 2H), 5.78–5.95 (m, 2H), 7.22–7.36

(m, 5H); ¹³C NMR (67.8 MHz, CDCl₃) d 21.4, 25.0, 25.4,

27.1, 46.3, 52.6, 123.0, 127.3, 128.0, 128.6, 133.0, 135.2,

137.4, 143.5, 172.1; EI-LRMS m/z 253 (M^þ), 224, 162, 91;

EI-HRMS m/z calcd for C₁₇H₁₉ON (M^þ) 253.1467, found

253.1463.

4.4.2. (5aS ^p,8aS ^p,8bR ^p)-1-(Toluene-4-sulfonyl)-2,4,5,

5a,7,8,8a,8b-octahydro-1H-benzo[cd]indol-6-one (11).

To a suspension of Dess–Martin periodinane (77 mg,

0.18 mmol) in CH₂Cl₂(0.5 mL) was added a solution of

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

7385

1

alcohol (40 mg, 0.12 mmol) in CH₂Cl₂(0.7 mL) at 0 8C, and

the solution was stirred at room temperature for 1 h. To this

solution was added saturated NaHCO₃aq. and saturated

Na₂S₂O₃aq., and the aqueous layer was extracted with

ether. The organic layer was washed with brine, dried over

Na₂SO₄, and evaporated. The residue was puriﬁed by

column chromatography on silica gel (hexane/ethyl acetate

3:1) to yield 10 and 11 as an inseparable mixture. This

mixture was allowed at room temperature to give 11 (35 mg,

88%) as colorless needles. Mp 136.5–139 8C. (Ethyl

1162 cm²¹; H NMR (270 MHz, CDCl₃) d 1.26–2.23 (m,

8H), 1.68 (t, J¼2.4 Hz, 3H), 2.42 (s, 3H), 3.93–4.10 (m,

2H), 4.56 (br, 1H), 5.52 (m, 1H), 5.70–5.79 (m, 1H), 7.27

(d, J¼8.3 Hz, 2H), 7.77 (d, J¼8.3 Hz, 2H); ¹³C NMR

(67.8 MHz, CDCl₃) d 3.5 (CH₃), 21.5 (CH₃), 26.3 (CH₂),

27.6 (CH₂), 28.2 (CH₂), 33.2 (CH₂), 33.7 (CH₂), 59.6 (CH),

75.2 (C), 80.1 (C), 127.5 (CH£2), 129.2 (CH£2), 132.3

(CH), 133.4 (CH), 138.2 (C), 142.9 (C); LRMS m/z 317

(M^þ), 249, 234, 162, 155, 94, 91; HRMS calcd for

C₁₈H₂₃NO₂S (M^þ) 317.1449, found 317.1442. Anal. calcd

for C₁₈H₂₃NO₂S: C, 68.10; H, 7.30; N, 4.41; S, 10.10.

Found: C, 68.08; H, 7.18; N, 4.37; S, 10.15.

acetate/hexane); IR (ﬁlm) n 1713, 1598, 1341, 1164 cm²¹

;

¹H NMR (400 MHz, CDCl₃) d 1.24–1.33 (m, 1H), 1.86–

1.98 (m, 2H), 2.08–2.16 (m, 2H), 2.24–2.37 (m, 3H), 2.43

(s, 3H), 2.60 (m, 1H), 2.79 (br, 1H), 3.79–3.83 (m, 1H),

3.91 (d, J¼13.2 Hz, 1H), 4.24 (ddd, J¼13.2, 8.0, 5.2 Hz,

1H), 5.61 (br, 1H), 7.33 (d, J¼8.0 Hz, 2H), 7.75 (d, J¼

8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃) d 20.9 (CH₂),

21.0 (CH₂), 21.6 (CH₃), 28.5 (CH₂), 36.6 (CH₂), 41.9

(CH), 42.3 (CH), 51.1 (CH₂), 58.2 (CH), 121.6 (CH),

127.4 (CH£2), 129.7 (CH£2), 134.0 (C), 134.7 (C), 143.6

(C), 209.9 (C); LRMS m/z 331 (M^þ), 274, 176, 155, 120,

91; HRMS calcd for C₁₈H₂₁NO₃S (M^þ) 331.1242,

found 331.1233. Anal. calcd for C₁₈H₂₁NO₃S: C, 65.23;

H, 6.39; N, 4.23; S, 9.68. Found: C, 65.03; H, 6.40; N, 4.22;

S, 9.52.

4.6.3. N-But-2-ynyl-N-cyclooct-2-enyl-4-methyl-ben-

zenesulfonamide (2c). A colorless solid. Mp 85–87 8C.

(Ethyl acetate/hexane); IR (nujol) n 2214, 1648, 1597, 1333,

1

1162 cm²¹; H NMR (270 MHz, CDCl₃) d 1.32–1.77 (m,

8H), 1.67 (t, J¼2.4 Hz, 3H), 2.11–2.21 (m, 2H), 2.40 (s,

3H), 3.96–4.16 (m, 2H), 4.79–4.88 (m, 1H), 5.54–5.62 (m,

2H), 7.24 (d, J¼8.3 Hz, 2H), 7.75 (d, J¼8.3 Hz, 2H); ¹³C

NMR (67.8 MHz, CDCl₃) d 3.4 (CH₃), 21.5 (CH₃), 24.6

(CH₂), 26.1 (CH₂), 26.2 (CH₂), 29.0 (CH₂), 33.5 (CH₂), 34.5

(CH₂), 55.6 (CH), 75.1 (C), 80.2 (C), 127.6 (CH£2), 128.4

(CH), 129.0 (CH£2), 130.1 (CH), 138.0 (C), 142.8 (C);

LRMS m/z 331 (M^þ), 249, 234, 176, 155, 94, 91; HRMS

calcd for C₁₉H₂₅NO₂S (M^þ) 331.1606, found 331.1631.

Anal. calcd for C₁₉H₂₅NO₂S: C, 68.85; H, 7.60; N, 4.23; S,

9.67. Found: C, 68.87; H, 7.56; N, 4.24; S, 9.66.

4.5. Typical procedure for the preparation of

cycloalkene-yne 2

To a suspension of NaH (60% oil suspension, 147 mg,

3.6 mmol) in THF/DMF (5 mL each) was added a solution

of 3a (673 mg, 3.0 mmol) in THF/DMF (5 mL each) at 0 8C,

and the solution was stirred at room temperature for 60 min.

To this solution was added 3-bromocyclohexene (0.4 mL,

3.6 mmol). The whole solution was warmed at 40 8C for

4.5 h. To this solution was added saturated NH₄Cl aq., and

the aqueous layer was extracted with ethyl acetate. The

organic layer was washed with brine, dried over Na₂SO₄,

and evaporated. The residue was puriﬁed by column

chromatography on silica gel (hexane/ether 5:1) to yield

2a (900 mg, quant.) as a colorless solid.

4.6.4. N-Cyclohex-2-enyl-4-methyl-N-prop-2-ynyl-ben-

zenesulfonamide (2d). A colorless solid; IR (nujol) n

1

2116, 1653, 1596, 1332, 1157 cm²¹; H NMR (270 MHz,

CDCl₃) d 1.52–1.98 (m, 6H), 2.16 (t, J¼2.4 Hz, 1H), 2.42

(s, 3H), 3.91 (dd, J¼18.4, 2.4 Hz, 1H), 4.13 (dd, J¼18.4,

2.4 Hz, 1H), 4.46–4.51 (m, 1H), 5.29–5.33 (m, 1H), 5.86–

5.91 (m, 1H), 7.28 (d, J¼8.4 Hz, 2H), 7.81 (d, J¼8.4 Hz,

2H); ¹³C NMR (67.8 MHz, CDCl₃) d 21.4 (CH₂), 21.5

(CH₃), 24.3 (CH₂), 28.0 (CH₂), 32.6 (CH₂), 55.1 (CH), 72.0

(CH), 80.6 (C), 127.0 (CH), 127.4 (CH£2), 129.4 (CH£2),

133.2 (CH), 137.9 (C), 143.2 (C); LRMS m/z 289 (M^þ),

155, 134, 91; HRMS calcd for C₁₆H₁₉NO₂S (M^þ) 289.1136,

found 289.1126. Anal. calcd for C₁₆H₁₉NO₂S: C, 66.40; H,

6.62; N, 4.84; S, 11.08. Found: C, 66.46; H, 6.58; N, 4.89; S,

11.04.

4.6. Spectral data for cycloalkene-yne 2

4.6.1. N-But-2-ynyl-N-cyclohex-2-enyl-4-methyl-ben-

zenesulfonamide (2a). A colorless solid. Mp 84–86 8C.

4.6.5. N-Cyclohept-2-enyl-4-methyl-N-prop-2-ynyl-ben-

zenesulfonamide (2e). A colorless oil; IR (neat) n 2120,

1654, 1598, 1336, 1160 cm²¹; ¹H NMR (270 MHz, CDCl₃)

d 1.30–2.24 (m, 8H), 2.17 (t, J¼2.4 Hz, 1H), 2.42 (s, 3H),

4.01 (d, J¼2.4 Hz, 1H), 4.14 (d, J¼2.4 Hz, 1H), 4.56 (br,

1H), 5.49 (m, 1H), 5.71–5.81 (m, 1H), 7.27 (d, J¼8.1 Hz,

2H), 7.78 (d, J¼8.1 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃)

d 21.5 (CH₃), 26.2 (CH₂), 27.3 (CH₂), 28.1 (CH₂), 33.1

(CH₂), 33.2 (CH₂), 59.7 (CH), 72.2 (CH), 80.1 (C), 127.4

(CH£2), 129.4 (CH£2), 132.7 (CH), 132.9 (CH), 137.8 (C),

143.2 (C); LRMS m/z 303 (M^þ), 155, 148, 91; HRMS calcd

for C₁₇H₂₁NO₂S (M^þ) 303.1293, found 303.1282. Anal.

calcd for C₁₇H₂₁NO₂S: C, 67.29; H, 6.98; N, 4.62; S, 10.57.

Found: C, 67.10; H, 6.93; N, 4.60; S, 10.58.

(Ether/hexane); IR (ﬁlm) n 2225, 1647, 1334, 1160 cm²¹

;

¹H NMR (270 MHz, CDCl₃) d 1.68 (t, J¼2.4 Hz, 3H),

1.74–1.81 (m, 4H), 1.95 (br, 2H), 2.42 (s, 3H), 3.83–4.09

(m, 2H), 4.49 (br, 1H), 5.30–5.33 (m, 1H), 5.83–5.87 (m,

1H), 7.27 (d, J¼8.3 Hz, 2H), 7.81 (d, J¼8.3 Hz, 2H); ¹³C

NMR (100 MHz, CDCl₃) d 3.4 (CH₃), 21.4 (CH₃), 21.4

(CH₂), 24.3 (CH₂), 27.9 (CH₂), 33.1 (CH₂), 54.9 (CH), 75.5

(C), 79.6 (C), 127.1 (CH), 127.2 (CH£2), 129.0 (CH£2),

132.5 (CH), 138.1 (C), 142.7 (C); LRMS m/z 303 (M^þ),

155, 148, 91; HRMS calcd for C₁₇H₂₁NO₂S (M^þ) 303.1293,

found 303.1287. Anal. calcd for C₁₇H₂₁NO₂S: C, 67.29; H,

6.98; N, 4.62; S, 10.57. Found: C, 67.22; H, 6.82; N, 4.54; S,

10.56.

4.6.2. N-But-2-ynyl-N-cyclohept-2-enyl-4-methyl-ben-

zenesulfonamide (2b). A colorless solid. Mp 93–96 8C.

(Ether/hexane); IR (nujol) n 2213, 1647, 1596, 1336,

4.6.6. N-Cyclooct-2-enyl-4-methyl-N-prop-2-ynyl-ben-

zenesulfonamide (2f). The title compound was prepared

in quantitative yield according to the literature procedure.^7c

7386

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

4.6.7. N-Cyclohex-2-enyl-4-methyl-N-pent-3-ynyl-ben-

zenesulfonamide (2g). A colorless oil; IR (neat) n 2934,

1598, 1494, 1448, 1393, 1340, 1233, 1161, 1097,

(s, 3H), 4.68 (t, J¼5.7 Hz, 1H), 5.35 (t, J¼5.7 Hz, 1H), 5.89

(d, J¼5.4 Hz, 1H), 5.97 (d, J¼5.4 Hz, 1H); ¹³C NMR

(67.8 MHz, CDCl₃) d 24.8 (CH₃), 24.7 (CH₃), 18.0 (C),

25.8 (CH₃£3), 40.9 (CH₂), 54.5 (CH₃), 74.6 (CH), 80.4

(CH), 130.5 (CH), 139.4 (CH), 155.4 (C); LRMS m/z 271

(M^þ2H), 215, 197, 171, 151, 133, 125, 111; HRMS calcd

for C₁₃H₂₃O₄Si (M^þ2H) 271.1365, found 271.1363.

1

1044 cm²¹; H NMR (270 MHz, CDCl₃) d 1.47–1.96 (m,

6H), 1.77 (t, J¼2.4 Hz, 3H), 2.42 (s, 3H), 2.36–2.70 (m,

2H), 3.01–3.29 (m, 2H), 4.45 (m, 1H), 5.01–5.05 (m, 1H),

5.75–5.80 (m, 1H), 7.29 (d, J¼8.4 Hz, 2H), 7.73 (d, J¼

8.4 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d 3.4 (CH₃),

21.5 (CH₃), 21.7 (CH₂), 22.3 (CH₂), 24.4 (CH₂), 28.9 (CH₂),

43.6 (CH₂), 55.4 (CH), 76.12 (C), 77.4 (C), 127.1 (CH),

127.4 (CH£2), 129.7 (CH£2), 132.5 (CH), 137.8 (C), 143.1

(C); LRMS m/z 317 (M^þ), 302, 288, 264, 250, 236, 184,

182, 155, 91; HRMS calcd for C₁₈H₂₃NO₂S (M^þ) 317.1449,

found 317.1455.

4.7.3. N-{(1R ^p,4S ^p)-4-(tert-Butyl-dimethylsilanyloxy)-

cyclohex-2-enyl}-4-methyl-N-prop-2-ynyl-benzenesul-

fonamide (7a). To a solution of 6a (430 mg, 1.5 mmol), 3b

(337 mg, 1.6 mmol), and PPh₃(37 mg, 0.15 mmol) in THF

(15 mL) was added Pd₂dba₃·CHCl₃(37 mg, 0.04 mmol),

and the solution was degassed through freeze–pump–thaw

cycle. The whole solution was stirred at room temperature

for 48 h. The solvent was removed, and the residue was

puriﬁed by ﬂash column chromatography on silica gel

(hexane/ethyl acetate 20:1–10:1) to yield 7a (471 mg, 75%)

as colorless needles. IR (ﬁlm) n 2121, 1654, 1598, 1338,

1255, 1163, 1093 cm²¹; ¹H NMR (270 MHz, CDCl₃) d 0.04

(s, 6H), 0.87 (s, 9H), 1.56–1.72 (m, 3H), 2.01–2.08 (m,

1H), 2.14 (t, J¼2.4 Hz, 1H), 2.42 (s, 3H), 3.95 (dd, J¼18.4,

2.7 Hz, 1H), 4.06 (m, 1H), 4.11 (dd, J¼18.4, 2.7 Hz, 1H),

4.35–4.40 (m, 1H), 5.41 (dd, J¼10.0, 2.4 Hz, 1H), 5.83–

5.89 (m, 1H), 7.28 (d, J¼8.4 Hz, 2H), 7.81 (d, J¼8.4 Hz,

2H); ¹³C NMR (67.8 MHz, CDCl₃) d 24.8 (CH₃), 24.5

(CH₃), 18.0 (C), 21.5 (CH₃), 22.5 (CH₂), 25.8 (CH₃£3),

30.4 (CH₂), 32.9 (CH₂), 54.7 (CH), 63.0 (CH), 72.1 (CH),

80.3 (C), 127.5 (CH£2), 129.1 (CH), 129.5 (CH£2), 135.0

(CH), 137.9 (C), 143.3 (C); LRMS m/z 404 (M^þ2CH₃), 362,

266, 155, 132, 117, 91; HRMS calcd for C₁₈H₂₄NO₃SSi

(M^þ2Bu) 362.1246, found 362.1233. Anal. calcd for

C₂₂H₃₃NO₃SSi: C, 62.97; H, 7.93; N, 3.34; S, 7.64.

Found: C, 63.05; H, 7.80; N, 3.22; S, 7.59.

4.6.8. N-But-3-ynyl-N-cyclohex-2-enyl-4-methyl-ben-

zenesulfonamide (2h). A colorless crystals. Mp 66–

67 8C; IR (nujol) n 3277, 2968, 2867, 1697, 1648, 1597,

1493, 1450, 1336, 1238, 1198, 1162, 1097 cm²¹; ¹H NMR

(270 MHz, CDCl₃) d 1.46–1.62 (m, 2H), 1.75–1.96 (m,

4H), 2.02 (t, J¼2.7 Hz, 1H), 2.42 (s, 3H), 2.46–2.78 (m,

2H), 3.07–3.34 (m, 2H), 4.45 (m, 1H), 5.03 (m, 1H), 5.76–

5.82 (m, 1H), 7.30 (d, J¼8.1 Hz, 2H), 7.73 (d, J¼8.1 Hz,

2H); ¹³C NMR (67.8 MHz, CDCl₃) d 21.4 (CH₃), 21.6

(CH₂), 21.9 (CH₂), 24.3 (CH₂), 28.8 (CH₂), 43.0 (CH₂), 55.3

(CH), 70.0 (C), 81.3 (CH), 127.0 (CH), 127.1 (CH£2),

129.7 (CH£2), 132.7 (CH), 137.6 (C), 143.2 (C); LRMS m/z

303 (M^þ), 264, 249, 184, 155, 148, 108, 91. Anal. calcd for

C₁₇H₂₁NO₂S: C, 67.29; H, 6.98; N, 4.62. Found: C, 67.15;

H, 7.08; N, 4.73.

4.7. Synthesis of cycloalkene-yne 7

4.7.1. Carbonic acid (1R ^p, 4S ^p)-4-(tert-butyl-dimethyl-

silanyloxy)-cyclohex-2-enyl ester methyl ester (6a). A

solution of 5a (789 mg, 3.45 mmol) in CH₂Cl₂(17 mL) was

added pyridine (0.84 mL, 10.4 mmol), methyl chloro-

formate (0.53 mL, 6.9 mmol) at 0 8C, and the solution was

stirred at 0 8C for 1 h. To this solution was added water, and

the aqueous layer was extracted with ethyl acetate. The

organic layer was washed with brine, dried over Na₂SO₄,

and evaporated. The residue was puriﬁed by column

chromatography on silica gel (hexane/ethyl acetate 9:1) to

yield 6a (988 mg, quant.) as a colorless oil. IR (neat) n 1747,

1472, 1462, 1442, 1395, 1360, 1344, 1321, 1309, 1270,

1224, 1205, 1149, 1094, 1046, 1025, 1005 cm²¹; ¹H NMR

(270 MHz, CDCl₃) d 0.07 (s, 6H), 0.89 (s, 9H), 1.72–2.00

(m, 4H), 3.77 (s, 3H), 4.16 (br, 1H), 5.01 (br, 1H), 5.78 (dd,

J¼3.8, 10.3 Hz, 1H), 5.89 (dd, J¼2.7, 10.3 Hz, 1H); ¹³C

NMR (67.8 MHz, CDCl₃) d 24.7 (CH₃), 24.6 (CH₃), 18.0

(C), 25.3 (CH₂), 25.8 (CH₃£3), 28.2 (CH₂), 54.5 (CH₃),

66.2 (CH), 70.9 (CH), 125.4 (CH), 136.9 (CH), 155.4 (C);

LRMS m/z 229 (M^þ2Bu), 211, 185, 151, 133; HRMS calcd

for C₁₀H₁₇O₄Si (M^þ2Bu) 229.0896, found 229.0880. Anal.

calcd for C₁₄H₂₆O₄Si: C, 58.70; H, 9.15. Found: C, 58.73;

H, 9.20.

4.7.4. N-[(1R ^p,4S ^p)-4-(tert-Butyl-dimethyl-silanyloxy)-

cyclopent-2-enyl]-4-methyl-N-prop-2-ynyl-benzene-

sulfonamide (7c). A colorless crystal. Mp 97.5 8C (EtOAc/

hexane); IR (nujol) n 3261, 2925, 2855, 2120, 1594, 1330,

1

1154 cm²¹; H NMR (270 MHz, CDCl₃) d 0.02 (s, 6H),

0.84 (s, 9H), 1.57 (m, 1H), 2.08 (t, J¼2.4 Hz, 1H), 2.41 (s,

3H), 2.46 (m, 1H), 4.02 (brs, 2H), 4.58 (br, 1H), 4.80 (br,

1H), 5.63 (m, 1H), 5.87 (m, 1H), 7.27 (d, J¼8.6 Hz, 2H),

7.79 (d, J¼8.6 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃)

d 24.8 (CH₃), 24.7 (CH₃), 18.0 (C), 21.5 (CH₃), 25.8

(CH₃£3), 32.4 (CH₂), 38.7 (CH₂), 61.8 (CH), 71.9 (C), 74.6

(CH), 80.7 (CH), 127.5 (CH£2), 129.4 (CH£2), 131.6 (CH),

137.5 (C), 138.2 (CH), 143.3 (C); LRMS m/z 405 (M^þ),

390, 348, 308, 250, 155, 139, 118, 91. Anal. calcd for

C₂₁H₃₁NO₃SSi: C, 62.18; H, 7.70; N, 3.45. Found: C, 61.97;

H, 7.69; N, 3.47.

4.7.5. N-{(1S ^p,4S ^p)-4-(tert-Butyl-dimethylsilanyloxy)-

cyclohex-2-enyl}-4-methyl-N-prop-2-ynyl-benzenesul-

fonamide (7b). To a solution of 5a (437 mg, 1.92 mmol),

3b (570 mg, 2.88 mmol), and PPh₃(1.03 g, 3.83 mmol) in

THF (10 mL) was added DEAD (0.6 mL, 3.83 mmol) at

0 8C, and the solution was stirred at room temperature for

10 h. The solvent was removed, and the residue was puriﬁed

by ﬂash column chromatography on silica gel (hexane/ethyl

acetate 9:1) to yield 7b (500 mg, 62%) as a colorless oil. IR

4.7.2. Carbonic acid (1R ^p,4S ^p)-4-(tert-butyl-dimethyl-

silanyloxy)-cyclopent-2-enyl ester methyl ester (6b). A

colorless oil; IR (neat) n 1748, 1472, 1462, 1443, 1375,

1361, 1335, 1268, 1193, 1132, 1098, 1048, 1007 cm²¹; ¹H

NMR (270 MHz, CDCl₃) d 0.06 (s, 6H), 0.86 (s, 9H), 1.65

(dt, J¼13.9, 7.3 Hz, 1H), 2.80 (dt, J¼13.9, 7.3 Hz, 1H), 3.74

(neat) n 2120, 1654, 1598, 1338, 1162 cm²^{1 1}H NMR

;

(400 MHz, CDCl₃) d 0.05 (s, 6H), 0.87 (s, 9H), 1.47–1.56

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

7387

(m, 1H), 1.73–1.83 (m, 1H), 1.87–1.91 (m, 1H), 1.97–2.01

(m, 1H), 2.17 (t, J¼2.4 Hz, 1H), 2.42 (s, 3H), 3.88 (dd,

J¼18.4, 2.4 Hz, 1H), 4.07 (dd, J¼18.4, 2.4 Hz, 1H), 4.24

(m, 1H), 4.50 (m, 1H), 5.29 (dd, J¼10.4, 1.6 Hz, 1H), 5.74

(dd, J¼10.4, 2.0 Hz, 1H), 7.27 (d, J¼8.0 Hz, 2H), 7.78 (d,

J¼8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃) d 24.7 (CH₃),

24.5 (CH₃), 18.2 (C), 21.6 (CH₃), 25.9 (CH₃£3), 27.0

(CH₂), 32.5 (CH₂), 32.7 (CH₂), 55.3 (CH), 66.9 (CH), 72.3

(CH), 80.3 (C), 127.3 (CH£2), 127.8 (CH), 129.4 (CH£2),

137.5 (C), 137.6 (CH), 143.3 (C); LRMS m/z 404

(M^þ2CH₃), 362, 288, 264, 155, 132, 91; HRMS calcd for

C₁₈H₂₄NO₃SSi (M^þ2Bu) 362.1246, found 362.1230. Anal.

calcd for C₂₂H₃₃NO₃SSi: C, 62.97; H, 7.93; N, 3.34; S, 7.64.

Found: C, 62.83; H, 7.72; N, 3.16; S, 7.67.

14d–e. Et₃N (0.30 mL, 2.13 mmol) and ClPO(OEt)₂

(0.17 mL, 1.16 mmol) was added to a solution of 13d

(108.5 mg, 0.97 mmol) in CH₂Cl₂(5 mL) at 0 8C. After

stirring for 1 h at the same temperature, propargylamine

(0.10 mL, 1.45 mmol) was added. The resulting solution

was stirred for 22 h at room temperature. Saturated

NaHCO₃solution was added, and the aqueous phase was

extracted with AcOEt. The organic phase was washed with

saturated NH₄Cl solution and brine, and dried over MgSO₄,

ﬁltered, and concentrated. The residue was puriﬁed by

column chromatography on silica gel (hexane/AcOEt 3:2)

to afford crude amide (89.7 mg, 62%). A solution of crude

amide (260 mg, 1.74 mmol) in DMF (6 mL) was added to a

suspension of NaH (85 mg, 2.09 mmol) in DMF (3 mL) at

0 8C. After stirring for 1 h at room temperature, BnBr

(0.33 mL, 2.79 mmol) was added at 0 8C. The resulting

solution was stirred for 30 min at room temperature.

Saturated NH₄Cl solution was added, and the aqueous

phase was extracted with AcOEt. The organic phase was

washed with H₂O and brine, and dried over MgSO₄, ﬁltered,

and concentrated. The residue was puriﬁed by column

chromatography on silica gel (hexane/AcOEt 3:1) to afford

14d (353 mg, 85%) as a pale yellow oil.

4.7.6. N-[(1S ^p,4S ^p)-4-(tert-Butyl-dimethyl-silanyloxy)-

cyclopent-2-enyl]-4-methyl-N-prop-2-ynyl-benzenesul-

fonamide (7d). A colorless oil; IR (neat) n 3277, 2954,

2930, 2856, 2361, 2344, 1598, 1339, 1162 cm²¹; ¹H NMR

(270 MHz, CDCl₃) d 0.02 (s, 6H), 0.84 (s, 9H), 1.84 (m,

1H), 2.07 (t, J¼2.4 Hz, 1H), 2.13 (m, 1H), 2.41 (s, 3H), 3.78

(dd, J¼18.9, 2.4 Hz, 1H), 3.97 (dd, J¼18.9, 2.4 Hz, 1H),

4.98 (m, 1H), 5.20 (m, 1H), 5.55–5.59 (m, 1H), 5.89–5.93

(m, 1H), 7.27 (d, J¼8.4 Hz, 2H), 7.77 (d, J¼8.4 Hz, 2H);

¹³C NMR (67.8 MHz, CDCl₃) d24.7 (CH₃£2), 18.1 (C),

21.5 (CH₃), 25.8 (CH₃£3), 32.5 (CH₂), 38.4 (CH₂), 63.3

(CH), 72.2 (C), 76.3 (CH), 79.9 (CH), 127.5 (CH£2), 129.5

(CH£2), 131.8 (CH), 137.3 (C), 139.6 (CH), 143.4 (C);

LRMS m/z 405 (M^þ), 390, 348, 250, 155, 139, 118, 91;

HRMS calcd for C₂₀H₂₈NO₃SSi (M^þ2Me) 390.1559,

found 390.1547. Anal. calcd for C₂₁H₃₁NO₃SSi: C, 62.18;

H, 7.70; N, 3.45; S, 7.91. Found: C, 61.99; H, 7.68; N, 3.42;

S, 8.08.

4.9. Spectral data for 14

4.9.1. N-Cyclopent-1-enylmethyl-4-methyl-N-prop-2-

ynyl-benzenesulfonamide (14a). A colorless crystal. Mp

55.5 8C. (Ether/hexane); IR (nujol) n 3259, 2923, 2114,

1654, 1596, 1343, 1160 cm²¹; ¹H NMR (270 MHz, CDCl₃)

d 1.89 (dt, J¼7.3 Hz, 2H), 1.97 (t, J¼2.4 Hz, 1H), 2.24–

2.36 (m, 4H), 2.42 (s, 3H), 3.86 (s, 2H), 4.04 (d, J¼2.4 Hz,

2H), 5.69 (brs, 1H), 7.28 (d, J¼8.1 Hz, 2H), 7.74 (d, J¼

8.1 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d 21.5 (CH₃),

23.4 (CH₂), 32.5 (CH₂), 33.0 (CH₂), 35.6 (CH₂), 46.5 (CH₂),

73.5 (CH), 76.7 (C), 127.8 (CH£2), 129.4 (CH£2), 130.6

(CH), 136.1 (C), 138.2 (C), 143.4 (C); LRMS m/z 289 (M^þ),

155, 134, 91. Anal. calcd for C₁₆H₁₉NO₂S: C, 66.41; H,

6.62; N, 4.84; S, 11.08. Found: C, 66.42; H, 6.73; N, 4.79; S,

11.14.

4.8. Typical procedure for the preparation of

cycloalkene-yne 14

To a solution of 13a (2.2 mL, 17.3 mmol) in CH₂Cl₂

(49 mL) was added DIBAL-H (42 mL, 39 mmol, 0.93 M in

hexane), and the solution was stirred at 278 8C for 1 h. To

this solution was added MeOH and 3 N NaOH aq. at 278 8C

and the aqueous layer was extracted with Et₂O. The organic

layer was washed with brine, dried over Na₂SO₄and

evaporated. To a solution of the crude alcohol in CH₂Cl₂

(32 mL) were added CBr₄(6.5 g, 19.5 mmol) and PPh₃

(5.9 g, 22.5 mmol), and the solution was stirred at room

temperature for 2 h. To a solution of propargyl bromide

(5.9 mL, 86 mmol) and K₂CO₃(9.6 g, 69 mmol) in CH₃CN

(115 mL) was added the above solution, and the whole

solution was stirred at room temperature for 16 h. Then the

solution was ﬁltered through Celite. To this mother liquid

was added pyridine (15.5 mL, 193 mmol) and p-toluene-

sulfonyl chloride (24.5 g, 130 mmol), and the solution was

stirred at room temperature for 25 h. To this solution was

added MeOH and the solution was diluted with ethyl

acetate. The organic layer was washed with 10% HCl aq.,

10% NaOH aq., and brine, dried over Na₂SO₄and

evaporated. After the solvent was removed, the residue

was puriﬁed by ﬂash column chromatography on silica gel

(hexane/ethyl acetate 5:1) to yield 14a (2.3 g, 45%) as a

colorless crystal.

4.9.2. N-Cyclohex-1-enylmethyl-4-methyl-N-prop-2-

ynyl-benzenesulfonamide (14b). A colorless crystal. Mp

54–54.5 8C. (Ether/hexane); IR (nujol) n 3292, 2926, 2853,

1596, 1346, 1158 cm²¹; ¹H NMR (270 MHz, CDCl₃) d 1.57

(m, 4H), 1.94 (t, J¼2.4 Hz, 1H), 1.99 (m, 4H), 2.42 (s, 3H),

3.67 (s, 2H), 4.02 (d, J¼2.4 Hz, 2H), 5.68 (s, 1H), 7.28 (J¼

8.4 Hz, 2H), 7.73 (d, J¼8.4 Hz, 2H); ¹³C NMR (67.8 MHz,

CDCl₃) d 21.5 (CH₃), 22.2 (CH₂), 22.5 (CH₂), 25.2 (CH₂),

25.8 (CH₂), 35.2 (CH₂), 52.8 (CH₂), 73.4 (CH), 76.6 (C),

127.6 (CH), 127.8 (CH£2), 129.3 (CH£2), 131.6 (C), 136.2

(C), 143.3 (C); LRMS m/z 303 (M^þ), 288, 222, 155, 148, 91;

HRMS calcd for C₁₇H₂₁NO₂S (M^þ) 303.1293, found

303.1303. Anal. calcd for C₁₇H₂₁NO₂S: C, 67.29; H, 6.98;

N, 4.62; S, 10.57. Found: C, 67.11; H, 7.13; N, 4.47; S,

10.71.

4.9.3. N-Cyclohept-1-enylmethyl-4-methyl-N-prop-2-

ynyl-benzenesulfonamide (14c). A colorless crystal. Mp

72–73 8C. (Ether/hexane); IR (nujol) n 3304, 2922, 2852,

1654, 1597, 1348, 1163 cm²¹; ¹H NMR (270 MHz, CDCl₃)

d 1.48–1.54 (m, 4H), 1.69 (m, 2H), 1.92 (t, J¼2.4 Hz, 1H),

2.08–2.21 (m, 4H), 2.42 (s, 3H), 3.65 (s, 2H), 4.04 (d,

Typical procedure for the preparation of cycloalkene-yne

7388

T. Kitamura et al. / Tetrahedron 60 (2004) 7375–7389

3. Preliminary reports: (a) Kitamura, T.; Mori, M. Org. Lett.

2001, 3, 1161. (b) Mori, M.; Kuzuba, Y.; Kitamura, T.; Sato,

Y. Org. Lett. 2002, 4, 3855. For reports from our laboratory;

(c) Kinoshita, A.; Mori, M. Synlett 1994, 1020. (d) Kinoshita,

A.; Mori, M. J. Org. Chem. 1996, 61, 8356. (e) Kinoshita, A.;

Mori, M. Heterocycles 1997, 46, 287. (f) Mori, M.;

Sakakibara, N.; Kinoshita, A. J. Org. Chem. 1998, 63, 6082.

(g) Kinoshita, A.; Sakakibara, N.; Mori, M. J. Am. Chem. Soc.

1997, 119, 12388. (h) Kinoshita, A.; Sakakibara, N.; Mori, M.

Tetrahedron 1999, 55, 8155. (i) Mori, M.; Kitamura, T.;

Sakakibara, N.; Sato, Y. Org. Lett. 2000, 2, 543. (j) Mori, M.;

Kitamura, T.; Sato, Y. Synthesis 2001, 654. (k) Kitamura, T.;

Sato, Y.; Mori, M. Chem. Commun. 2001, 1258. (l) Kitamura,

T.; Sato, Y.; Mori, M. Adv. Synth. Catal. 2002, 344, 678.

(m) Mori, M.; Tonogaki, K.; Nishiguchi, N. J. Org. Chem.

2002, 67, 224. (n) Saito, N.; Sato, Y.; Mori, M. Org. Lett.

2002, 4, 803. (o) Tonogaki, K.; Mori, M. Tetrahedron Lett.

2002, 43, 2235.

J¼2.4 Hz, 2H), 5.79 (m, 1H), 7.28 (d, J¼8.4 Hz, 2H), 7.74

(d, J¼8.4 Hz, 2H); ¹³C NMR (67.8 MHz, CDCl₃) d 21.5

(CH₃), 26.7 (CH₂), 27.0 (CH₂), 28.5 (CH₂), 30.0 (CH₂), 32.2

(CH₂), 35.1 (CH₂), 54.4 (CH₂), 73.6 (CH), 77.2 (C), 127.9

(CH£2), 129.3 (CH£2), 132.9 (CH), 136.2 (C), 137.7 (C),

143.3 (C); LRMS m/z 317 (M^þ), 162, 155, 91. Anal. calcd

for C₁₆H₁₉NO₂S: C, 68.10; H, 7.30; N, 4.41; S, 10.10.

Found: C, 68.00; H, 7.28; N, 4.46; S, 10.16.

4.9.4. N-Benzyl-N-(prop-2-ynyl)-1-cyclopentene-1-carb-

oxamide (14d). A pale yellow oil; IR (neat) n 2120 (w),

1

1714 (s), 1644 (s), 1606 (s), 1454 (s), 1244 (s) cm²¹; H

NMR (270 MHz, CDCl₃) d 1.93 (tt, J¼7.5, 7.5 Hz, 2H),

2.25 (br, 1H), 2.43–2.52 (br, 2H), 2.63–2.72 (m, 2H),

4.06–4.14 (br, 2H), 4.75 (s, 2H), 6.08 (br, 1H), 7.24–7.37

(m, 5H); ¹³C NMR (67.8 MHz, DMSO) d 21.9, 32.4, 33.6,

35.4, 48.6, 73.7, 78.9, 126.5, 126.7, 127.7, 131.6, 136.4,

137.3, 167.7; EI-LRMS m/z 239 (M^þ), 211, 200, 95, 91;

EI-HRMS m/z calcd for C₁₆H₁₇ON (M^þ) 239.1310, found

239.1297.

4. Ruthenium carbene systems; (a) Kim, S.-H.; Bowden, N.;

Grubbs, R. H. J. Am. Chem. Soc. 1994, 116, 10801.

(b) Stragies, R.; Schuster, M.; Blechert, S. Angew. Chem.

Int. Ed. Engl. 1997, 36, 2518. (c) Barrett, A. G. M.; Baugh,

S. P. D.; Braddock, D. C.; Flack, K.; Gibson, V. C.; Giles,

M. R.; Marshall, E. L.; Procopiou, P. A.; White, A. J. P.;

Williams, D. J. J. Org. Chem. 1998, 63, 7893. (d) Hoye, R. T.;

Donaldoson, S. M.; Vos, T. Org. Lett. 1999, 1, 277.

(e) Stragies, R.; Voigtmann, U.; Blechert, S. Tetrahedron

Lett. 2000, 41, 5465. (f) Bentz, D.; Laschat, S. Synthesis 2000,

1766. (g) Bentz, D.; Laschat, S. Synthesis 2000, 1766.

(h) Kulkarni, A. A.; Diver, S. T. Org. Lett. 2000, 2, 2271.

(i) Schramm, M. P.; Reddy, D. S.; Kozmin, S. A. Angew.

Chem. Int. Ed. 2001, 40, 4274. (j) Fu¨rstner, A.; Ackermann, L.;

Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer,

F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236. (k) Timmer, M. S.

M.; Ovaa, H.; Filippov, D. V.; van der Marel, G. A.; van

Boom, J. H. Tetrahedron Lett. 2001, 42, 8231. (l) Yao, Q. Org.

Lett. 2001, 3, 2069. (m) Smulik, J. A.; Giessert, A. J.; Diver,

S. T. Tetrahedron Lett. 2002, 43, 209. (n) Layton, M. E.;

Morales, C. A.; Shair, M. D. J. Am. Chem. Soc. 2002, 124, 773.

(o) Poulsen, C. S.; Madsen, R. J. Org. Chem. 2002, 67, 4441.

(p) Micalizio, G. C.; Schreiber, S. L. Angew. Chem. Int. Ed.

2002, 41, 3272. (q) Hansen, E. C.; Lee, D. J. Am. Chem. Soc.

2003, 1125, 9582. (r) Katritzky, A. R.; Nair, S. K.; Khokhlova,

T.; Akhmedov, N. G. J. Org. Chem. 2003, 68, 5724. (s) Yang,

Y.-K.; Tae, J. Synlett 2003, 2013. (t) Lee, H.-Y.; Kim, H. Y.;

Tae, H.; K, B. G.; Lee, J. Org. Lett. 2003, 5, 3439. (u) Kulkarni,

A. A.; Diver, S. T. Org. Lett. 2003, 5, 3463. (v) Giessert, A. J.;

Brazis, N. J.; Diver, S. T. Org. Lett. 2003, 5, 3819.

4.9.5. N-Benzyl-N-(prop-2-ynyl)-1-cyclohexene-1-carb-

oxamide (14e). A colorless liquid; IR (neat) n 2118 (w),

;

1621 (s), 1495 (m), 1451 (s), 1239 (s) cm²^{1 1}H NMR

(270 MHz, CDCl₃) d 1.58–1.75 (m, 4H), 2.07–2.15 (m,

2H), 2.23–2.30 (m, 3H), 4.04–4.10 (br, 2H), 4.73 (s, 2H),

5.99 (br, 1H), 7.23–7.37 (m, 5H); ¹³C NMR (67.8 MHz,

DMSO) d 20.7, 21.1, 23.6, 24.9, 35.6, 48.5, 73.7, 78.9,

126.6, 126.9, 126.9, 127.9, 133.4, 136.6, 171.3; EI-LRMS

m/z 253 (M^þ), 214, 109, 91; EI-HRMS m/z calcd for

C₁₇H₁₉ON (M^þ) 253.1467, found 253.1467.

References and notes

1. (a) Grubbs, R. H. Handbook of Metathesis; Wiley-VCH:

Weinheim, 2003. Recent reviews for oleﬁn metathesis;

(b) Grubbs, R. H.; Miller, S. J. Acc. Chem. Res. 1995, 28,

446. (c) Schuster, M.; Blechert, S. Angew. Chem. Int. Ed. Engl.

1997, 36, 2036. (d) Schmalz, H.-G. Angew. Chem. Int. Ed.

Engl. 1995, 34, 1833. (e) Fu¨rstner, A. Topics in Organo-

metallic Chemistry; Springer: Berlin, 1998; Vol. 1. (f) Grubbs,

R. H.; Chang, S. Tetrahedron 1998, 54, 4413. (g) Armstrong,

S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371. (h) Phillips,

A. J.; Abell, A. D. Aldrichim. Acta 1999, 32, 75. (i) Fu¨rstner,

A. Angew. Chem. Int. Ed. 2000, 39, 3013. (j) Trnka, T. M.;

Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18. (k) Schrock, R. R.;

Hoveyda, A. H. Angew. Chem. Int. Ed. 2003, 42, 4592.

(l) Connnon, S. J.; Blechert, S. Angew. Chem. Int. Ed. 2003,

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Organomet. Chem. 1998, 1, 133. (n) Mori, M. J. Synth. Org.

Chem. Jpn 1998, 56, 115. (o) Poulsen, C. S.; Madsen, R.

Synthesis 2003, 1.

5. Review on cycloisomerization of enynes; (a) Trost, B. M.;

Krische, M. J. Synlett 1998, 1. For selected other examples;

(b) Katz, T. J.; Sivavec, T. M. J. Am. Chem. Soc. 1985, 107,

737. (c) Trost, B. M.; Tanoury, G. J. J. Am. Chem. Soc. 1988,

110, 1636. (d) Mori, M.; Watanuki, S. J. Chem. Soc., Chem.

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Organometallics 1994, 13, 4129. (f) Chatani, N.; Morimoto,

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(g) Fu¨rstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc.

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Chem. Soc. 2001, 123, 11863. (i) Ackermann, L.; Bruneau, C.;

Dixneuf, P. H. Synlett 2001, 397. (j) Semeril, D.; Cleran, M.;

Bruneau, C.; Dixneuf, P. H. Adv. Synth. Catal. 2001, 343, 184.

6. Examples; (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L.

J. Am. Chem. Soc. 1995, 117, 9610. (b) Schneider, M. F.;

2. For 1a; (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs,

R. H. Angew. Chem. Int. Ed. Engl. 1995, 34, 2039. For 1b;

(b) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett.

1999, 1, 953. For 1c; (c) Weskamp, T.; Schattenmann, W. C.;

Spiegler, M.; Herrmann, W. A. Angew. Chem. Int. Ed. 1998,

37, 2490. (d) Huang, J.; Stevens, E. D.; Nolan, S. P.; Peterson,

J. L. J. Am. Chem. Soc. 1999, 121, 2674. (e) Scholl, M.; Trnka,

T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett. 1999,

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¨ ¨

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8. Recently, Blechert et al. reported the similar reaction using

Article Doi

ROM-RCM of cycloalkene-yne

DOI: 10.1016/j.tet.2004.05.030

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