Oxidative transformation of tert-cyclobutanols by palladium catalysis under oxygen atmosphere

Article abstract of DOI:10.1021/jo0016475

Palladium(II)-catalyzed oxidative reaction of tert-cyclobutanols involving the cleavage of a C - C bond via β-carbon elimination under atmospheric pressure of oxygen is described. An alkylpalladium intermediate produced by β-carbon elimination from a Pd(I

Full text of DOI:10.1021/jo0016475

J . Org. Chem. 2001, 66, 1455-1465
1455
Oxid a tive Tr a n sfor m a tion of ter t-Cyclobu ta n ols by P a lla d iu m
Ca ta lysis u n d er Oxygen Atm osp h er e
Takahiro Nishimura, Kouichi Ohe, and Sakae Uemura*
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University,
Sakyo-ku, Kyoto 606-8501, J apan
uemura@scl.kyoto-u.ac.jp
Received November 20, 2000
Palladium(II)-catalyzed oxidative reaction of tert-cyclobutanols involving the cleavage of a C-C
bond via â-carbon elimination under atmospheric pressure of oxygen is described. An alkylpalladium
intermediate produced by â-carbon elimination from a Pd(II) alcoholate gives a variety of products,
depending on the substituents on the cyclobutane ring, in which reactions such as dehydrogenative
ring opening, ring expansion and ring contraction are involved. For some substrates, the addition
of a catalytic amount of ethyl acrylate dramatically accelerates the reaction. In all cases, the
dehydrogenative products are obtained and the Pd(II)-hydride species produced at the final stage
can be converted again to active Pd(II) species by molecular oxygen.
In tr od u ction
Pd19-22 and Pt,23 and Zn24 have been used for their
reactions. Among several types of a selective C-C bond
cleavage reaction, the catalytic â-dealkylation from late
transition metal alkyl complexes involving cyclobutane
or cyclopropane group is a class of the most interesting
processes to construct an M-C bond for successive
reaction affording useful organic compounds.5,7c,12,14,15,20c-h
On the other hand, catalytic reactions involving â-alkyl
elimination from the late transition metal alcoholates25
have also been developed for the past few years, although
their examples are still limited.26-28 For example, Tamaru
and co-workers demonstrated that â-carbon elimination
via a π-allylpalladium alcoholate intermediate generated
The transformation of small ring compounds permits
the development of synthetic strategy to various useful
compounds in organic synthesis because of the unique
reactivity provided by the ring strain.1 Especially, transi-
tion metal catalyzed reactions utilizing the cleavage of a
C-C bond in small ring compounds2a,c have been devel-
oped in recent years, as well as the unstrained C-C bond
cleavage reactions,2 and various kinds of soluble late
transition metals such as Ru,3-5 Co,6 Rh,7-15 Ir,16 Ni,17,18
(1) For reviews, see: (a) Small Ring Compounds in Organic Syn-
thesis I-IV. In Topics in Current Chemistry; de Meijere, A., Ed.;
Springer-Verlag: Berlin, 1986; Vol. 133; 1987; Vol. 135; 1988; Vol. 144;
1990; Vol. 155. (b) Durst, T.; Breau, L. In Comprehensive Organic
Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, U.K.,
1991; Vol. 5, pp 675-697. (c) Hudlicky, T.; Reed, J . W. In Comprehen-
sive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon:
Oxford, U.K., 1991; Vol. 5, pp 899-970. (d) Piers, E. In Comprehensive
Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford,
U.K., 1991; Vol. 5, pp 971-998. (e) Bronson, J . J .; Danheizer, R. L. In
Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon: Oxford, U.K., 1991; Vol. 5, pp 999-1035.
(2) For reviews, see: (a) Bishop, K. C., III. Chem. Rev. 1976, 76,
461. (b) Crabtree, R. H. Chem. Rev. 1985, 85, 245. (c) J ennings, P. W.;
J ohnson, L. L. Chem. Rev. 1994, 94, 2241. (d) Rybtchinski, B.; Milstein,
D. Angew. Chem., Int. Ed. 1999, 38, 870. (e) Murakami, M.; Ito, Y. In
Activation of Unreactive Bonds and Organic Synthesis; Murai, S., Ed.;
Springer: New York, 1999; pp 97-129.
(9) (a) Suggs, J . W.; J un, C.-H. J . Chem. Soc., Chem. Commun. 1985,
92. (b) J un, C.-H.; Lee, H. J . Am. Chem. Soc. 1999, 121, 880.
(10) Kaneda, K.; Azuma, H.; Wayaku, M.; Teranishi, S. Chem. Lett.
1974, 215.
(11) Liou, S.-Y.; van der Boom, M. E.; Milstein, D. Chem. Commun.
1998, 687.
(12) Bessmertnykh, A. G.; Blinov, K. A.; Grishin, Y. K.; Donskaya,
N. A.; Tveritinova, E. V.; Yur‘eva, N. M.; Beletskaya, I. P. J . Org. Chem.
1997, 62, 6069 and references therein.
(13) Hayashi, M.; Ohmatsu, T.; Meng, Y.-P.; Saigo, K. Angew. Chem.,
Int. Ed. 1998, 37, 837.
(14) Huffman, M. A.; Liebeskind, L. S. J . Am. Chem. Soc. 1993, 115,
4895.
(15) (a) Wender, P. A.; Takahashi, H.; Witulski, B. J . Am. Chem.
Soc. 1995, 117, 4720. (b) Wender, P. A.; Husfeld, C. O.; Langkopf, E.;
Love, J . A. J . Am. Chem. Soc. 1998, 120, 1940. (c) Wender, P. A.;
Sperandio, D. J . Org. Chem. 1998, 63, 4164. (d) Wender, P. A.; Rieck,
H.; Fuji, M. J . Am. Chem. Soc. 1998, 120, 10976. (e) Wender, P. A.;
Glorius, F.; Husfeld, C. O.; Langkopf, E.; Love, J . A. J . Am. Chem.
Soc. 1999, 121, 5348. (f) Wender, P. A.; Dyckman, A. J .; Husfeld, C.
O.; Kadereit, D.; Love, J . A.; Rieck, H. J . Am. Chem. Soc. 1999, 121,
10442. (g) Wender, P. A.; Correa, A. G.; Sato, Y.; Sun, R. J . Am. Chem.
Soc. 2000, 122, 7815.
(3) (a) Mitsudo, T.; Zhang, S.-W.; Watanabe, Y. J . Chem. Soc., Chem.
Commun. 1994, 435. (b) Mitsudo, T.; Suzuki, T.; Zhang, S.-W.; Imai,
D.; Fujita, K.; Manabe, T.; Shiotsuki, M.; Watanabe, Y.; Wada, K.;
Kondo, T. J . Am. Chem. Soc. 1999, 121, 1839. (c) Kondo, T.; Nakamura,
A.; Okada, T.; Suzuki, N.; Wada, K.; Mitsudo, T. J . Am. Chem. Soc.
2000, 122, 6319.
(4) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J . Am. Chem. Soc.
1999, 121, 8645.
(5) Trost, B. M.; Toste, F. D.; Shen, H. J . Am. Chem. Soc. 2000, 122,
2379.
(6) Iwasawa, N.; Matsuo, T., Iwamoto, M.; Ikeno, T. J . Am. Chem.
Soc. 1998, 120, 3903.
(7) (a) Murakami, M.; Amii, H.; Ito, Y. Nature 1994, 370, 540. (b)
Murakami, M.; Amii, H.; Shigeto, K.; Ito, Y. J . Am. Chem. Soc. 1996,
118, 8285. (c) Murakami, M.; Takahashi, K.; Amii, H.; Ito, Y. J . Am.
Chem. Soc. 1997, 119, 9307. (d) Murakami, M.; Itahashi, T.; Amii, H.;
Takahashi, K.; Ito, Y. J . Am. Chem. Soc. 1998, 120, 9949. (e)
Murakami, M.; Tsuruta, T.; Ito, Y. Angew. Chem., Int. Ed. 2000, 39,
2484.
(8) (a) Perthuisot, C.; J ones, W. D. J . Am. Chem. Soc. 1994, 116,
3647. (b) Perthuisot, C.; Edelbach, B. L.; Zubris, D. L.; J ones, W. D.
Organometallics 1997, 16, 2018.
(16) Murakami, M.; Itami, K.; Ubukata, M.; Tsuji, I.; Ito, Y. J . Org.
Chem. 1998, 63, 4.
(17) (a) Noyori, R.; Odagi, T.; Takaya, H. J . Am. Chem. Soc. 1970,
92, 5780. (b) Noyori, R.; Kumagai, Y.; Umeda, I.; Takaya, H. J . Am.
Chem. Soc. 1972, 94, 4018. (c) Schwager, H.; Spyroudis, S.; Vollhardt,
K. P. C. J . Organomet. Chem. 1990, 382, 191. (d) Ryu, I.; Ikura, K.;
Tamura, Y.; Maenaka, J .; Ogawa, A.; Sonoda, N. Synlett 1994, 941.
(e) Huffman, M. A.; Liebeskind L. S. J . Am. Chem. Soc. 1991, 113,
2771.
(18) (a) Yoshikawa, S.; Aoki, K.; Kiji, J .; Furukawa, J . Tetrahedron
1974, 30, 405. (b) Golden, H. J .; Baker, D. J .; Miller, R. G. J . Am. Chem.
Soc. 1974, 96, 4235.
(19) Edelbach, B. L.; Lachicotte, R. J .; J ones, W. D. J . Am. Chem.
Soc. 1998, 120, 2843.
10.1021/jo0016475 CCC: $20.00 © 2001 American Chemical Society
Published on Web 01/23/2001

1456 J . Org. Chem., Vol. 66, No. 4, 2001
Nishimura et al.
Sch em e 1
from vinyl cyclic carbonate gave unsaturated aldehydes
and ketones.26 Kondo, Mitsudo, and co-workers reported
the ruthenium-catalyzed â-allyl elimination of tert-ho-
moallyl alcohols.27 Quite recently, the ring opening reac-
tions of tert-cyclopropanols were studied by two groups
independently.28
As a versatile strategy for the synthesis of ketones
using small ring compounds, a metal homoenolate is well-
established.29 The formation of a stable â-metallo ketone
(metal homoenolate) can be accomplished by the reaction
of siloxycyclopropanes with metal salts such as Ti, Hg,
Pt, Zn, Sn, etc. (eq 1), and further transformations of it
are possible to create a new C-C bond.29 In addition,
catalytic reactions involving â-metallo ketone were also
reported.22a-f,23b,28,29h
The formation of γ-metallo ketones from cyclobutanols
is an analogous process (eq 2), and this process may
become a new synthetic methodology.
transformation of tert-cyclobutanols to a variety of or-
ganic compounds via an organopalladium intermediate
I generated by â-carbon elimination from an initially
produced palladium(II) alcoholate (Scheme 1).31,32 Thus,
the fate of I leading to dehydrogenated products (II-V)
largely depends on the type of substituents on the
cyclobutane ring as shown in Scheme 1 and can be
exemplified with three types of reaction mode. When R4
) H, the dehydrogenative ring opening reaction proceeds
to afford unsaturated ketones (type 1, path a ). Type 2
reactions include the oxidative ring expansion to five- or
six-membered cyclic ketones (path b or c). Type 3
reactions represent the oxidative ring contraction en
route to a cyclopropane ring (path d ). In our preliminary
communication,31a we partly demonstrated the former
two types of reactions, and recently we found that the
oxidative ring contracting reaction of tert-cyclobutanols
proceeded to give cyclopropane derivatives. In this paper,
we describe the details of the type 3 reaction as well as
type 1 and 2 reactions in these oxidative transformations
of tert-cyclobutanols in the presence of a palladium
catalyst under atmospheric pressure of oxygen.
In the course of our studies on the aerobic oxidation of
alcohols by palladium catalysis,30 we found the novel
(20) For recent examples of the palladium-catalyzed reaction using
cyclopropane ring strain, see: (a) Lautens, M.; Ren, Y.; Delanghe, P.
H. M. J . Am. Chem. Soc. 1994, 116, 8821. (b) Lautens, M.; Ren, Y. J .
Am. Chem. Soc. 1996, 118, 10668. (c) Lautens, M.; Meyer, C.; Lorenz,
A. J . Am. Chem. Soc. 1996, 118, 10676. (d) Tsukada, N.; Shibuya, A.;
Nakamura, I.; Yamamoto, Y. J . Am. Chem. Soc. 1997, 119, 8123. (e)
Nakamura, I.; Itagaki, H.; Yamamoto, Y. J . Org. Chem. 1998, 63, 6458.
(f) Camacho, D. H.; Nakamura, I.; Saito, S.; Yamamoto, Y. Angew.
Chem., Int. Ed. 1999, 38, 3365. (g) Nakamura, I.; Saito, S.; Yamamoto,
Y. J . Am. Chem. Soc. 2000, 122, 2661. (h) de Meijere, A.; Bra¨se, S. J .
Organomet. Chem. 1999, 576, 88 and references therein.
(21) (a) Catellani, M.; Frignani, F.; Rangoni, A. Angew. Chem., Int.
Ed. Engl. 1997, 36, 119. (b) Catellani, M.; Cugini, F. Tetrahedron 1999,
55, 6595 and references therein. (c) Lautens, M.; Piguel, S. Angew.
Chem., Int. Ed. 2000, 39, 1045.
(22) (a) Aoki, S.; Fujimura, T.; Nakamura, E.; Kuwajima, I. J . Am.
Chem. Soc. 1988, 110, 3296. (b) Aoki, S.; Nakamura, E.; Kuwajima, I.
Tetrahedron Lett. 1988, 29, 1541. (c) Aoki, S.; Nakamura, E. Synlett
1990, 741. (d) Fujimura, T.; Aoki, S.; Nakamura, E. J . Org. Chem.
1991, 56, 2809. (e) Aoki, S.; Nakamura, E. Tetrahedron 1991, 47, 3935.
(f) Kang, S.-K.; Yamaguchi, T.; Ho, P.-S.; Kim, W.-Y.; Yoon, S.-K.
Tetrahedron Lett. 1997, 38, 1947. (g) Yasui, K.; Fugami, K.; Tanaka,
S.; Tamaru, Y.; Ii, A.; Yoshida, Z.; Saidi, M. R. Tetrahedron Lett. 1992,
33, 789.
(23) (a) Ikura, K.; Ryu, I.; Kambe, N.; Sonoda, N. J . Am. Chem. Soc.
1992, 114, 1520. (b) Hoberg, J . O.; J ennings, P. W. Organometallics
1996, 15, 3902. (c) Beyer, J .; Madsen, R. J . Am. Chem. Soc. 1998, 120,
12137.
Resu lts a n d Discu ssion
Deh yd r ogen a tive Rin g Op en in g Rea ction (Typ e
1). A Pd(II)-promoted or -catalyzed rearrangement of
(29) For reviews, see: (a) Murai, S.; Ryu, I.; Sonoda, N. J . Orga-
nomet. Chem. 1983, 250, 121. (b) Kuwajima, I.; Nakamura, E. Top.
Curr. Chem. 1990, 155, 1. (c) Kuwajima, I.; Nakamura, E. In
Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon: Oxford, U.K., 1991; Vol. 2, pp 441-454. For recent
representative examples, see: (d) Ikura, K.; Ryu, I.; Ogawa, A.; Sonoda,
N.; Harada, S.; Kasai, N. Organometallics 1991, 10, 528. (e) Nakahira,
H.; Ryu, I.; Ikebe, M.; Oku, Y.; Ogawa, A.; Kambe, N.; Sonoda, N.;
Murai, S. J . Org. Chem. 1992, 57, 17. (f) Ryu, I.; Matsumoto, K.;
Kameyama, Y.; Ando, M.; Kusumoto, N.; Ogawa, A.; Kambe, N.; Murai,
S.; Sonoda, N. J . Am. Chem. Soc. 1993, 115, 12330. (g) Kocˇovsky´, P.;
Sˇrogl, J .; Pour, M.; Gogoll, A. J . Am. Chem. Soc. 1994, 116, 186. (h)
Martins, E. O.; Gleason, J . L. Org. Lett. 1999, 1, 1643 and references
therein.
(30) (a) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron
Lett. 1998, 39, 6011. (b) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura,
S. J . Org. Chem. 1999, 64, 6750.
(31) (a) For palladium(II)-catalyzed oxidative ring cleavage of tert-
cyclobutanols, see: Nishimura, T.; Ohe, K.; Uemura, S. J . Am. Chem.
Soc. 1999, 121, 2645. (b) For palladium(0)-catalyzed arylation of tert-
cyclobutanols, see: Nishimura, T.; Uemura, S. J . Am. Chem. Soc. 1999,
121, 11010.
(24) Sugimura, T.; Futagawa, T.; Mori, A.; Ryu, I.; Sonoda, N.; Tai,
A. J . Org. Chem. 1996, 61, 6100 and references therein.
(25) (a) Collman, J . P.; Hegedus, L. S.; Norton, J . R.; Finke, R. G.
Principles and Applications of Organotransition Metal Chemistry;
University Science Books: Mill Valley, CA, 1989; pp 59-61. (b)
Crabtree, R. H. The Organometallic Chemistry of the Transition Metals,
2nd ed.; Wiley: New York, 1994; pp 57-59. (c) Bryndza, H. E.; Tam,
W. Chem. Rev. 1988, 88, 1163.
(26) Harayama, H.; Kuroki, T.; Kimura, M.; Tanaka, S.; Tamaru,
Y. Angew. Chem., Int. Ed. Engl. 1997, 36, 2352.
(27) Kondo, T.; Kodoi, K.; Nishinaga, E.; Okada, T.; Morisaki, Y.;
Watanabe, Y.; Mitsudo, T. J . Am. Chem. Soc. 1998, 120, 5587.
(28) For the oxidative ring opening reactions of tert-cyclopropanols
including â-carbon elimination from palladium(II) alcoholates produced
by the reaction of cyclopropanols and palladium(II) or palladium(0)
species, see: (a) Park, S.-B.; Cha, J . K. Org. Lett. 2000, 2, 147. (b)
Okumoto, H.; J innai, T.; Shimizu, H.; Harada, Y.; Mishima, H.; Suzuki,
A. Synlett 2000, 629. We had also found independently a similar
reaction of tert-cyclopropanols under oxygen atmosphere using our
catalytic conditions (unpublished results).
(32) For a recent review of the metal-mediated oxidation of tert-
alcohols, see: Wietzerbin, K.; Bernadou, J .; Meunier, B. Eur. J . Inorg.
Chem. 2000, 1391.

Oxidative Transformation of tert-Cyclobutanols
J . Org. Chem., Vol. 66, No. 4, 2001 1457
Ta ble 1. P a lla d iu m (II)-Ca ta lyzed Oxid a tive Rin g
Clea va ge Rea ction of Cyclobu ta n olsa
1-alkenyl or 1-alkynyl cyclobutanols to cyclopentanones
is a well-established method, and it has been applied to
the synthesis of a variety of natural products.33 This
reaction is promoted by the initial complexation of
palladium with alkenic or alkynic bond prior to migration
of a â-carbon in a cyclobutanol, in which usually a
secondary carbon atom can migrate more easily than a
primary one (eq 3).
In our initial communication,31a we reported that the
different bond-cleavage reaction proceeds via â-carbon
elimination to give a primary alkylpalladium intermedi-
ate as shown in Scheme 1.
First, the oxidative reaction of tert-cyclobutanols, in
which an alkylpalladium intermediate produced has
â-hydrogen available to be eliminated as shown in eq 4,
was carried out in the presence of Pd(OAc)2, pyridine,
ethyl acrylate, and MS3A at 80 °C under atmospheric
pressure of oxygen. In this type of reaction, a selective
C-C bond cleavage occurred to give â,γ- or R,â-unsatur-
ated ketones (Table 1).
The presence of ethyl acrylate was essential for the
efficient transformation, except for vinyl-substituted
cyclobutanols 1a and 2a (entries 1 and 4).34 It should be
noted that the reaction of butyl-substituted cyclobutanols
1c-6c could also smoothly proceed to give the corre-
sponding ketones in good yields. These results indicate
that the precoordination of palladium with the π-bond
is not required prior to C-C bond cleavage, compared
with the palladium(II)-mediated cyclobutane rearrange-
ment. The formation of a palladium(II) alcoholate is a
crucial step, and actually, tert-butyldimethylsilylated-1b
did not give any products. Bicyclic or tricyclic compounds
(1-3) yielded exo-methylene products (â,γ-unsaturated
ketones), while 435 and monocyclic ones (5 and 6) pro-
duced â,γ- and/or R,â-unsaturated ketones. In the cases
of 4 and 5 a Pd(II)-H species produced by the â-hydrogen
elimination might cause isomerization of an initially
formed â,γ-unsaturated ketones to R,â-enones. On the
other hand, in the case of 6 having a bulkier tert-butyl
group, the isomerization of the product was suppressed
to some extent (entries 13 and 14).
To know the role of ethyl acrylate, we examined the
reaction of 1b in the presence or absence of other acrylate
analogues (Table 2).
Substituents in an alkenic part of the acrylate de-
creased the reaction rate. Next, we investigated a time
course of the conversion of 1b to the product 7b (Figure
1). The time profile of the reaction of 1b in the presence
of ethyl acrylate showed a fine curve. On the other hand,
the reaction without ethyl acrylate was considerably slow
after ca. 0.5 h. When ethyl acrylate was added to the
reaction mixture after 1 h the reaction was accelerated
again. These observations suggest that the step of the
â-hydrogen elimination from an alkylpalladium inter-
mediate produced by â-carbon elimination might be
reversible and ethyl acrylate may expel an intramolecular
coordination of palladium with carbonyl oxygen to pro-
mote the reaction (eq 5).36
(33) For recent works on the palladium-catalyzed ring expansion of
cyclobutanols and cyclobutenols, see: (a) Clark, G. R.; Thiensathit, S.
Tetrahedron Lett. 1985, 26, 2503. (b) Liebeskind, L. S.; Mitchell, D.;
Foster, B. S. J . Am. Chem. Soc. 1987, 109, 7908. (c) Demuth, M.;
Pandey, B.; Wietfeld, B.; Said, H.; Viader, J . Helv. Chim. Acta 1988,
71, 1392. (d) de Almeida Barbosa, L.-C.; Mann, J . J . Chem. Soc., Perkin
Trans. 1 1990, 177. (e) Mitchell, D.; Liebeskind, L. S. J . Am. Chem.
Soc. 1990, 112, 291. (f) Nemoto, H.; Nagamochi, M.; Fukumoto, K. J .
Chem. Soc., Perkin Trans. 1 1993, 2329. (g) Nemoto, H.; Nagamochi,
M.; Ishibashi, H.; Fukumoto, K. J . Org. Chem. 1994, 59, 74. (h) Nemoto,
H.; Shiraki, M.; Fukumoto, K. Synlett 1994, 599. (i) Vo, N. H.; Snider,
B. B. J . Org. Chem. 1994, 59, 5419. (j) Nemoto, H.; Miyata, J .;
Fukumoto, K. Tetrahedron 1996, 52, 10363. (k) Nemoto, H.; Yoshida,
M.; Fukumoto, K. J . Org. Chem. 1997, 62, 6450. (l) Nemoto, H.; Miyata,
J .; Yoshida, M.; Raku, N.; Fukumoto, K. J . Org. Chem. 1997, 62, 7850.
(m) Kocˇovsky´, P.; Dunn, V.; Gogoll, A.; Langer, V. J . Org. Chem. 1999,
64, 101. (n) Yoshida, M.; Memoto, H.; Ihara, M. Tetrahedron Lett. 1999,
40, 8583. (o) Miyata, J .; Nemoto, H.; Ihara, M. J . Org. Chem. 2000,
65, 504. (p) Hegedus, L. S.; Ranslow, P. B. Synthesis 2000, 953. (q)
Yoshida, M.; Sugimoto, K.; Ihara, M. Tetrahedron Lett. 2000, 41, 5089.
(34) The addition of ethyl acrylate did not show a significant
difference in the yield of the products.
(35) In our preliminary communication (ref 31a), the structures of
4b and 10b were described incorrectly. The correct structures should
be as those described here (Table 1, entry 9).
The presence of oxygen was another crucial factor for
the reaction efficiency. When the reaction of 1b was

1458 J . Org. Chem., Vol. 66, No. 4, 2001
Nishimura et al.
Ta ble 2. Effect of Ad d itives
Sch em e 2
Sch em e 3
19 bearing a phenyl group instead of a vinyl group, the
ketone 2039 was obtained in high yield (eq 6).
F igu r e 1. Time profile of the reaction of tert-cyclobutanol 1b:
the reaction in the presence of ethyl acrylate (0.1 mmol) (4),
in the absence of ethyl acrylate (0), and in the presence of
ethyl acrylate (0.1 mmol) after 1 h (O).
The stereochemistry of 20 was confirmed by X-ray
crystallographic analysis, indicating that its ring juncture
was isomerized at some stage during the reaction (Figure
S1, Supporting Information).40 In this reaction, the
addition of ethyl acrylate did not affect both the reaction
rate and the yield of the product.
carried out under nitrogen atmosphere, the conversion
of 1b to 7b was only 10% after 16 h.37 We postulated that
a Pd(II)-H species produced by â-hydrogen elimination
from an alkylpalladium intermediate at the final stage
can react with molecular oxygen to give the Pd(II)-OOH
species, and this reactive species subsequently undergoes
ligand exchange with a tert-cyclobutanol to reproduce the
Pd(II) alcoholate and H2O2 as described in the oxidation
of primary and secondary alcohols under similar reaction
conditions.30b In fact, the formation of H2O2 was detected
by the qualitative test of an aqueous layer extracted from
the reaction mixture of 1b (after 6 h in the absence of
MS3A) with KI containing starch aqueous solution.
Oxid a tive Rin g Exp a n sion Rea ction (Typ e 2). The
reaction could be applied to vinyl-substituted bicyclic
cyclobutanols 13-15 having an angular substituent,
which blocks â-hydrogen elimination from the produced
alkylpalladium species (Scheme 2).
The formation of 20 can be explained by assuming the
reaction sequence shown in Scheme 3. An alkylpalladium
intermediate produced by â-carbon elimination undergoes
an intramolecular cyclization with the phenyl ring to give
a cis-organopalladium complex via a palladium enolate.
Successive â-hydrogen syn-elimination affords the prod-
uct 20. In this case, â-hydrogen elimination step might
be irreversible mainly as a result of the aromaticity of
the product, and thus the addition of ethyl acrylate did
not affect the reaction, compared with the reaction giving
unsaturated ketones (vide supra). Next, we examined the
behavior of cyclobutanols having either an electron-
withdrawing or electron-donating substituent on the
phenyl ring, the results of which are summarized in Table
3.41
4-Chlorophenyl-substituted cyclobutanol 21 yielded 26
in high yield (entry 2), although the reaction was slower
than that of the 4-methoxy-substituted one (entry 4).42
Interestingly, cyclobutanols 22 and 24 having a substitu-
In the reaction of these substrates cyclopentanones
were obtained. These results show that an alkylpalla-
dium intermediate undergoes cyclization in 5-exo mode
and subsequent â-hydrogen elimination to give a cyclo-
pentanone.38 On the other hand, in the case of substrate
(38) For these substrates, the effect of the addition of ethyl acrylate
was not observed.
(39) Thompson, H. W.; Long, D. J . J . Org. Chem. 1988, 53, 4201.
(40) A small amount (<5%) of cis-isomer was detected by 1H NMR
spectra of the crude reaction mixture.
(36) Similar effect using diphenylacetylene was observed in the
rhodium-catalyzed C-C bond activation of cyclobutanones (ref 7d).
(37) The formation of a palladium black was immediately observed.
(41) The stereochemistry of these products in Table 3 was confirmed
by 1H NMR.

Oxidative Transformation of tert-Cyclobutanols
J . Org. Chem., Vol. 66, No. 4, 2001 1459
Ta ble 3. P a lla d iu m (II)-Ca ta lyzed Oxid a tive Rin g
Exp a n sion Rea ction of Cyclobu ta n olsa
Ta ble 4. P a lla d iu m (II)-Ca ta lyzed Oxid a tive Rin g
Con tr a ctin g Rea ction of ter t-Cyclobu ta n olsa
to 1,3,3-trisubstituted cyclobutanols in order to obtain the
corresponding cyclohexanone derivatives (vide supra), the
unexpected ring contracting reaction took place to afford
cyclopropane derivatives (eq 7).
ent at the 3-position on the aromatic ring afforded
7-chloro- (27) and 7-methoxyhexahydroanthrathenone
(29) selectively and respectively, probably as a result of
the steric reason in the alkylpalladium species produced
from Pd(II) alcoholate (entries 3 and 5). 2-Naphthyl-
substituted cyclobutanol 25 also gave the ketone 30
selectively (entry 6). We also attempted the oxidation of
other cyclobutanols having a variety of substituents, such
as 3,5-bis(trifluoromethyl)phenyl, 2-methylphenyl, 2-meth-
oxyphenyl, 2-pyridyl, 3-pyridyl, and 2-furyl, but all
reactions failed.43
Thus, 2-phenylspiro[3.5]nonan-2-ol (31) afforded phen-
yl spiro[2.5]oct-1-yl ketone (37) almost quantitatively
(Table 4, entry 1).
The reaction was accelerated by the addition of a
catalytic amount of ethyl acrylate (entry 2). 1,3,3-Trisub-
stituted cyclobutanols 32-34 having a phenyl group or
a butyl group at the R-position of a hydroxyl group
afforded the corresponding cyclopropanes 38-40 in high
yields (entries 3-5). The reaction of cyclobutanols 35 and
36 bearing a phenyl group at the 3-position was sluggish,
and a longer reaction time was required. In these
reactions, the addition of ethyl acrylate was quite effec-
tive to obtain cyclopropanes 4144 and 4245 in sufficient
yields (entries 6-10). tert-Cyclobutanol 43 derived from
R-pinene gave a cyclopropane derivative as well (eq 8).
Oxid a tive Rin g Con tr a ctin g Rea ction (Typ e 3).
When the same procedure as described above was applied
(42) In the reaction of 23, cyclopropane 28′ was also isolated in 9%
yield, which might be formed via a Pd(IV) intermediate 28a or Pd-
carbene complex 28b produced by R-elimination.
(43) 3,5-Bis(trifluoromethyl)phenyl- or 2-pyridyl-substituted cyclo-
butanol did not afford any products, while the oxidation of 2-furyl,
2-methylphenyl, 2-methoxyphenyl or 3-pyridyl one was sluggish and
resulted in the formation of many unidentified products.
(44) A small amount of byproducts (ca. 5%) was also obtained, which
might be formed by the intermolecular reaction of an alkylpalladium
intermediate with ethyl acrylate.
(45) Each of the cis- and trans-isomers of 42 could be isolated and
each stereochemistry was confirmed by the observation of the NOE
spectra (methine proton and methyl proton, see Experimental Section).
For reviews of organopalladium(IV) chemistry, see: (a) Canty, A. J .
Acc. Chem. Res. 1992, 25, 83. (b) Canty, A. J . In Comprehensive
Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson,
G., Eds.; Pergamon: Oxford, U.K., 1995; Vol. 9, pp 225-290.

1460 J . Org. Chem., Vol. 66, No. 4, 2001
Nishimura et al.
In the absence of ethyl acrylate both the ring con-
tracted compound 44 and the ring opening product 45
were obtained, while in the presence of ethyl acrylate,
44 was produced selectively. The relationship between
the product yields and the reaction time was investigated
in the absence of ethyl acrylate (Figure 2). Figure 2 shows
that both compounds were produced competitively, show-
ing that 45 was not derived from 44.
F igu r e 2. Time profile of the reaction of 43.
Sch em e 4. P la u sible Rea ction P a th w a y
A plausible reaction pathway for the formation of
cyclopropanes is shown in Scheme 4 (ligands have been
omitted for clarity).46 The first step is the â-carbon
elimination from an initially produced palladium(II)
alcoholate to give an alkylpalladium(II) species A. Next,
a palladium enolate from the enol form of A is produced,
which may be in equilibrium with a palladacycle B. A
reductive elimination of a Pd(0) from the species B
affords the product cyclopropane.47,48 Similarly to the type
1 reaction, we propose that a divalent palladium species
such as a XPd(II)-OOH generated from XPdH and O2
works as an active species and reproduces a palladium-
(II) alcoholate and H2O2 by the reaction with an alcohol
in this cyclopropane formation. Actually, the generation
of H2O2 was detected by a simple KI/starch test in the
case of 31 (after 6 h in the absence of MS3A). Under the
present reaction conditions, the reoxidation of a Pd(0)
species to a Pd(II) species may take place by in situ
formed acetic acid and O2.49 In fact, when the oxidation
of 31 was carried out using Pd2(dba)3‚CHCl3 (10 mol %
Pd) as a catalyst in the presence of 20 mol % acetic acid
under oxygen, 48% conversion of 31 to the compound 37
was observed after 2 h (nearly the same value obtained
in the reaction using Pd(OAc)2), while the conversion of
31 was only 9% without acetic acid.50 The present
oxidative conditions favor the formation of AcOPdH in
equilibrium because of the stabilization effect of pyridine
for Pd(II)-H and Pd(II)-OOH species and also the facile
formation of AcOPdOOH with O2 (eq 9).51
The formation of 44 and 45 can be explained by
assuming the reaction sequence shown in Scheme 5. An
alkylpalladium intermediate C, produced by â-carbon
elimination, is converted into a palladacyclobutane E via
the formation of a palladium enolate D. Cyclopropane 44
can be produced by reductive elimination of Pd(0) from
the intermediate E, while â-hydrogen elimination from
E giving the species F followed by successive reductive
elimination results in the formation of the product 45.
The addition of ethyl acrylate probably increases the rate
of reductive elimination step as a π-acid in this ring
contraction.
(46) The formation of acetylcyclopropane from a γ-palladaketone
intermediate was reported, see: Ogoshi, S.; Morimoto, T.; Nishio, K.;
Ohe, K.; Murai, S. J . Org. Chem. 1993, 58, 9.
(47) For recent studies on catalytic cyclopropanation via reductive
elimination from palladacyclobutane, see: Satake, A.; Nakata, T. J .
Am. Chem. Soc. 1998, 120, 10391 and references therein.
(48) We may also assume an alternative pathway for this ring
contracting reaction via a Pd(IV) species (B′) considering from the
formation of cyclopropane 28′ obtained as a byproduct in the reaction
of 23 (ref 42), although details are not yet known.
(50) A 97% conversion of 31 in the presence of 10 mol % Pd2(dba)3‚
CHCl3 was observed after 23 h, in which an induction period (ca. 2 h)
was observed, whereas Pd(OAc)2 did not show any induction period.
This induction period shows two possible pathways for the oxidation
of Pd(0) to Pd(II). For a recent example of direct oxidation of Pd(0)
with oxygen, see ref 51c. For examples of oxidative addition of an
For recent example of Pd-catalyzed domino-reaction of bromodienynes
producing a cyclopropane ring under C-H activation, see: Schweizer,
S.; Song, Z.-Z.; Meyer, F. E.; Parsons, P. J .; de Meijere, A. Angew.
Chem., Int. Ed. 1999, 38, 1452. For the study of γ-elimination from a
dialkylplatinum complex affording a platinacyclobutane, see: Moore,
S. S.; DiCosimo, R.; Sowinski, A. F.; Whitesides, G. M. J . Am. Chem.
Soc. 1981, 103, 948.
(49) For examples of the formation of hydridopalladium(II) species
by the reaction of Pd(0) species and acetic acid or benzoic acid, see:
(a) Trost, B. M.; Rise, F. J . Am. Chem. Soc. 1987, 109, 3161. (b) Kadota,
I.; Shibuya, A.; Lutete, L. M.; Yamamoto, Y. J . Org. Chem. 1999, 64,
4570 and references therein.
alcoholic O-H bond to Pd(0) to produce
a hydridopalladium(II)
alcoholate, see: (a) Braga, D.; Sabatino, P.; Di Bugno, C.; Leoni, P.;
Pasquali, M. J . Organomet. Chem. 1987, 334, C46. (b) Di Bugno, C.;
Pasquali, M.; Leoni, P.; Sabatino, P.; Braga, D. Inorg. Chem. 1989,
28, 1390.
(51) (a) Igersheim, F.; Mimoun, H. Nouv. J . Chim. 1980, 4, 711. (b)
Hosokawa, T.; Murahashi, S.-I. Acc. Chem. Res. 1990, 23, 49. (c) ten
Brink, G.-J .; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287,
1636.

Oxidative Transformation of tert-Cyclobutanols
J . Org. Chem., Vol. 66, No. 4, 2001 1461
2H), 7.51-7.56 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 22.0,
22.1, 22.8, 24.1, 26.2, 37.9, 43.1, 75.3, 125.7, 127.3, 128.4, 146.7.
Anal. Calcd for C14H18O: C, 83.12; H, 8.97. Found: C, 82.84;
H, 8.94.
Sch em e 5. P la u sible Rea ction P a th w a y
7-Bu tylbicyclo[4.2.0]octa n -7-ol (1c). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 0.93 (t, J ) 6.8 Hz, 3H), 1.01-1.13
(m, 1H), 1.25-1.70 (m, 14H), 1.86-2.01(m, 3H), 2.12 (ddd, J
) 17.6, 8.3, 2.9 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.2,
21.8, 22.7, 23.2, 24.2, 26.0, 26.1, 37.3, 39.6, 42.3, 73.3. Anal.
Calcd for C12H22O: C, 79.06; H, 12.16. Found: C, 78.79; H,
12.25.
8-Vin ylbicyclo[5.2.0]n on a n -8-ol (2a ). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 0.98-1.28 (m, 3H), 1.39 (q, J ) 11.7
Hz, 1H), 1.55-1.89 (m, 7H), 1.94-2.03 (m, 1H), 2.10-2.21 (m,
1H), 2.33-2.41 (m, 2H), 5.01 (dd, J ) 10.7, 1.0 Hz, 1H), 5.21
(dd, J ) 17.1, 1.0 Hz, 1H), 6.11 (dd, J ) 17.1, 10.7 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 24.7, 28.9, 29.7, 30.9, 32.0, 34.2,
40.9, 49.5, 72.1, 110.0, 144.5. Anal. Calcd for C11H18O: C,
79.47; H, 10.91. Found: C, 79.73; H, 10.79.
1
8-P h en ylbicyclo[5.2.0]n on a n -8-ol (2b). Colorless oil; H
Con clu sion s
NMR (270 MHz, CDCl3) δ 0.98-1.35 (m, 3H), 1.50-2.04 (m,
9H), 2.18-2.34 (m, 1H), 2.68-2.80 (m, 2H), 7.21-7.28 (m, 1H),
7.31-7.39 (m, 2H), 7.45-7.50 (m, 2H); 13C NMR (67.8 MHz,
CDCl3) δ 25.3, 29.2, 29.6, 32.1, 32.1, 34.1, 41.4, 50.4, 74.1,
124.7, 126.9, 128.4, 148.1. Anal. Calcd for C15H20O: C, 83.29;
H, 9.32. Found: C, 83.00; H, 9.47.
Several transformations of tert-cyclobutanols to afford
oxidative products by palladium(II) catalysis using at-
mospheric pressure of oxygen as a sole reoxidant are
described. â-Carbon elimination from a Pd(II) alcoholate
proceeds to give an alkylpalladium intermediate, which
shows an interesting reactivity to afford several types of
products. Although more detailed studies are required
to solve the question of mechanism for some steps
including â-carbon elimination, these results demonstrate
the interesting possibility and utility of palladium ca-
talysis using â-carbon elimination in organic synthesis.
8-Bu tylbicyclo[5.2.0]n on a n -8-ol (2c). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 0.92 (t, J ) 7.3 Hz, 3H), 0.95-1.40
(m, 8H), 1.44-1.66 (m, 7H), 1.72-1.87 (m, 3H), 1.93-2.25 (m,
3H); 13C NMR (100 MHz, CDCl3) δ 14.2, 23.2, 25.1, 25.5, 28.9,
30.0, 31.1, 32.0, 34.4, 41.3, 41.5, 49.5, 72.1. Anal. Calcd for
C
13H24O: C, 79.53; H, 12.32. Found: C, 79.38; H, 12.13.
3-P h en yl-exo-tr icyclo[4.2.1.02,5]n on a n -3-ol (3b). White
1
solid; mp 66.5-66.9 °C; H NMR (270 MHz, CDCl3) δ 1.00-
1.15 (m, 2H), 1.34 (d, J ) 10.3 Hz, 1H), 1.50-1.58 (m, 2H),
1.88 (s, OH, 1H), 2.00 (dd, J ) 13.1, 5.8 Hz, 1H), 2.07-2.19
(m, 1H), 2.16 (br s, 1H), 2.27 (d, J ) 10.3 Hz, 1H), 2.35 (br s,
1H), 2.45 (d, J ) 5.8 Hz, 1H), 2.55 (ddd, J ) 13.1, 8.3, 2.2 Hz,
1H), 7.20-7.27 (m, 1H), 7.36 (t, J ) 7.6 Hz, 2H), 7.53 (dd, J )
7.6, 1.7 Hz, 2H); 13C NMR (67.8 MHz, CDCl3) δ 28.2, 28.3, 34.1,
34.5, 35.5, 38.9, 40.1, 55.0, 74.8, 124.0, 126.6, 128.3, 149.4.
Anal. Calcd for C15H18O: C, 84.07; H, 8.47. Found: C, 84.00;
H, 8.63.
Exp er im en ta l Section
Gen er a l Meth od s. 1H NMR spectra were obtained in
CDCl3 at 270 or 400 MHz with Me4Si as an internal standard.
The following abbreviations are used: s, singlet; d, doublet; t,
triplet; q, quartet; qui, quintet; sxt, sextet; m, multiplet. 13C
NMR spectra were obtained at 67.8 or 100 MHz. Melting
points are uncorrected. GLC yields were determined using
bibenzyl or biphenyl as an internal standard. Elemental
analysis was done at the Microanalytical Center of Kyoto
University.
Ma t er ia ls. Pd(OAc)2 was purchased from Wako Pure
Chemical Ind. Ltd. and used without further purification. Pd2-
(dba)3‚CHCl352 (dba ) dibenzylideneacetone) was synthesized
by the literature method. Pyridine was purchased and used
without further purification. Solvents were dried and distilled
by known methods. MS3A (powder) was commercially avail-
able from Nacalai Tesque, which was activated by calcination
(by a gas burner) just before use. Cyclobutanols were prepared
from the corresponding cyclobutanones and Grignard reagent
or alkyllithium. Cyclobutanones were prepared by the reduc-
tion of R,R-dichlorocyclobutanones synthesized by the reported
procedure53 in the presence of Zn powder and AcOH.54
7-Vin ylbicyclo[4.2.0]octa n -7-ol (1a ). Colorless oil; 1H
NMR (270 MHz, CDCl3) δ 1.11-1.80 (m, 9H), 2.00-2.18 (m,
3H), 2.22-2.32 (m, 1H), 5.08 (dd, J ) 10.7, 1.4 Hz, 1H), 5.29
(dd, J ) 17.3, 1.4 Hz, 1H), 6.19 (dd, J ) 17.3, 10.7 Hz, 1H);
13C NMR (67.8 MHz, CDCl3) δ 21.6, 21.8, 22.7, 23.5, 25.9, 37.0,
42.5, 73.2, 111.1, 143.4. Anal. Calcd for C10H16O: C, 78.90; H,
10.59. Found: C, 78.64; H, 10.57.
3-Bu tyl-exo-tr icyclo[4.2.1.02,5]n on an -3-ol (3c). White solid;
1
mp 38.3-38.5 °C; H NMR (400 MHz, CDCl3) δ 0.92 (t, J )
7.3 Hz, 3H), 0.97-1.09 (m, 2H), 1.20-1.40 (m, 5H), 1.40-1.60
(m, 6H), 1.85-1.92 (m, 1H), 1.95-2.07 (m, 3H), 2.04 (br s, 1H),
2.19 (br s, 1H); 13C NMR (100 MHz, CDCl3) δ 14.2, 23.1, 24.9,
28.1, 28.4, 33.7, 33.8, 35.2, 37.8, 38.8, 43.2, 52.7, 73.9. Anal.
Calcd for C13H22O: C, 80.36; H, 11.41. Found: C, 80.07; H,
11.34.
2,3-Ben zo-6-p h en ylb icyclo[3.2.0]h ep t -2-en -7-ol (4b ).
1
White solid; mp 55.0-55.5 °C; H NMR (400 MHz, CDCl3) δ
1.80 (s, OH, 1H), 2.24 (ddd, J ) 13.2, 3.9, 1.0 Hz, 1H), 3.13
(dd, J ) 17.1, 9.3 Hz, 1H), 3.21 (ddd, J ) 13.2, 8.3, 1.5 Hz,
1H), 3.46-3.57 (m, 2H), 3.73 (td, J ) 8.3, 3.9 Hz, 1H), 7.18-
7.33 (m, 5H), 7.35-7.42 (m, 2H), 7.50-7.54 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ 32.6, 39.0, 45.5, 49.1, 75.9, 124.5, 124.7,
124.9, 126.9, 126.9, 127.0, 128.4, 145.0, 147.5. Anal. Calcd for
C
17H16O: C, 86.41; H, 6.82. Found: C, 86.27; H, 6.75.
2,3-Ben zo-6-bu tylbicyclo[3.2.0]h ept-2-en -7-ol (4c). White
1
solid; mp 37.6-38.0 °C; H NMR (400 MHz, CDCl3) δ 0.94 (t,
J ) 7.3 Hz, 3H), 1.30-1.41 (m, 4H), 1.47 (br s, OH, 1H), 1.58-
1.68 (m, 2H), 1.80 (dd, J ) 12.7, 4.9 Hz, 1H), 2.63 (ddd, J )
12.7, 8.5, 1.7 Hz, 1H), 2.99-3.08 (m, 2H), 3.25-3.35 (m, 1H),
7-P h en ylbicyclo[4.2.0]octa n -7-ol (1b). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 1.14-1.26 (m, 1H), 1.42-1.60 (m,
5H), 1.68-1.94 (m, 3H), 1.96-2.06 (m, 1H), 2.29 (dd, J ) 11.2,
10.6 Hz, 1H), 2.49 (ddd, J ) 11.2, 7.8, 4.4 Hz, 1H), 2.69 (ddd,
J ) 16.8, 8.3, 4.4 Hz, 1H), 7.25-7.31 (m, 1H), 7.34-7.40 (m,
3.47-3.54 (m, 1H), 7.12-7.18 (m, 3H), 7.24-7.28 (m, 1H); 13
C
NMR (100 MHz, CDCl3) δ 14.2, 23.1, 25.3, 32.2, 38.6, 42.2,
44.2, 47.3, 74.3, 124.2, 124.9, 126.5, 126.7, 145.0, 148.0. Anal.
Calcd for C15H20O: C, 83.29; H, 9.32. Found: C, 83.02; H, 9.24.
3-Hexyl-1-p h en ylcyclobu ta n ol (5b, cis/tr a n s ) 67/33).
Colorless oil; 1H NMR (400 MHz, CDCl3) δ 0.88 (t, J ) 6.8
Hz), 1.15-1.35 (m), 1.41 (q, J ) 6.8 Hz, 1H, trans-isomer), 1.50
(q, J ) 6.8 Hz, 1H, cis-isomer), 1.75-1.90 (m, 1H, cis-isomer),
1.92-2.05 (m, 2H, cis-isomer), 2.05-2.18 (m, 2H, trans-
isomer), 2.40-2.47 (m, 2H, trans-isomer), 2.54-2.68 (m, 1H,
(52) Ukai, T.; Kawazura, H.; Ishii, Y.; Bonnet, J . J .; Ibers, J . A. J .
Organomet. Chem. 1974, 65, 253.
(53) Krepski, L. R.; Hassner, A. J . Org. Chem. 1978, 43, 2879.
(54) (a) Grieco, P. A. J . Org. Chem. 1972, 37, 2363. (b) Greene, A.
E.; Luche, M.-J .; Serra, A. A. J . Org. Chem. 1985, 50, 3957.

1462 J . Org. Chem., Vol. 66, No. 4, 2001
Nishimura et al.
trans-isomer), 2.69-2.75 (m, 2H, cis-isomer), 7.22-7.40 (m),
7.51-7.55 (m). Anal. Calcd for C16H24O: C, 82.70; H, 10.41.
Found: C, 82.60; H, 10.70.
20.9, 21.3, 22.8, 28.3, 31.7, 35.9, 48.3, 48.9, 76.7, 123.0, 125.3,
126.9, 129.7, 134.3, 150.3. Anal. Calcd for C15H19ClO: C, 71.85;
H, 7.64. Found: C, 72.12; H, 7.59.
1-Bu tyl-3-h exylcyclobu ta n ol (5c, cis/tr a n s ) 67/33).
Colorless oil; 1H NMR (400 MHz, CDCl3) δ 0.88 (t, J ) 7.3
Hz), 0.93 (t, J ) 6.8 Hz), 1.15-1.44 (m), 1.47-1.75 (m), 2.03-
2.10 (m, 2H, trans-isomer), 2.16-2.24 (m, 2H, cis-isomer), 2.35
(sept, J ) 7.8 Hz). Anal. Calcd for C14H28O: C, 79.18; H, 13.29.
Found: C, 79.48; H, 13.25.
7-(4-Met h oxyp h en yl)-1-m et h ylb icyclo[4.2.0]oct a n -7-
ol (23). Colorless oil; 1H NMR (400 MHz, CDCl3) δ 1.09 (s,
3H), 1.20-1.34 (m, 1H), 1.46-1.75 (m, 6H), 1.82-1.90 (m, 1H),
1.93-2.04 (m, 1H), 2.14 (d, J ) 12.2 Hz, 1H), 2.26 (d, J ) 12.2
Hz, 1H), 2.35 (br dd, J ) 7.8, 2.4 Hz, 1H), 3.80 (s, 3H), 6.78 (d,
J ) 8.3 Hz, 2H), 7.31 (d, J ) 8.3 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 21.2, 21.4, 22.8, 28.4, 31.5, 35.9, 48.1, 48.7, 55.3, 76.6,
113.7, 126.1, 141.0, 158.5. Anal. Calcd for C16H22O2: C, 78.01;
H, 9.00. Found: C, 77.78; H, 9.16.
7-(3-Met h oxyp h en yl)-1-m et h ylb icyclo[4.2.0]oct a n -7-
ol (24). Colorless oil; 1H NMR (400 MHz, CDCl3) δ 1.11 (s,
3H), 1.20-1.33 (m, 1H), 1.50-1.75 (m, 6H), 1.85-1.90 (m, 1H),
1.95-2.05 (m, 1H), 2.14 (d, J ) 12.2 Hz, 1H), 2.29 (d, J ) 12.2
Hz, 1H), 2.36 (br dd, J ) 7.8, 2.4 Hz, 1H), 3.82 (s, 3H), 6.78
(dd, J ) 8.1, 2.4 Hz, 1H), 6.93-6.99 (m, 2H), 7.27 (dd, J ) 8.1,
8.1 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 21.1, 21.4, 22.9,
28.3, 31.5, 35.9, 48.1, 48.7, 55.2, 76.7, 110.9, 112.1, 117.2, 129.4,
150.2, 159.7. Anal. Calcd for C16H22O2: C, 78.01; H, 9.00.
Found: C, 77.92; H, 8.95.
1-Meth yl-7-(2-n aph th yl)bicyclo[4.2.0]octan -7-ol (25). Col-
orless oil; 1H NMR (400 MHz, CDCl3) δ 1.14 (s, 3H), 1.23-
1.38 (m, 1H), 1.50-1.80 (m, 5H), 1.83 (br s, OH, 1H), 1.88-
1.97 (m, 1H), 1.99-2.10 (m, 1H), 2.23 (d, J ) 12.2 Hz, 1H),
2.40 (d, J ) 12.2 Hz, 1H), 2.49 (br dd, J ) 7.8, 2.4 Hz, 1H),
7.40-7.50 (m, 2H), 7.53 (dd, J ) 8.8, 2.0 Hz, 1H), 7.76-7.84
(m, 4H); 13C NMR (100 MHz, CDCl3) δ 21.1, 21.4, 22.8, 28.4,
31.7, 36.0, 48.0, 48.6, 77.1, 122.8, 123.9, 125.8, 126.1, 127.5,
128.1, 128.3, 132.4, 133.1, 145.5. Anal. Calcd for C19H22O: C,
85.67; H, 8.32. Found: C, 85.45; H, 8.35.
3-ter t-Bu tyl-1-p h en ylcyclobu ta n ol (6b, cis/tr a n s ) 65/
35). White solid; 1H NMR (400 MHz, CDCl3) δ 0.85 (s, 9H,
trans-isomer), 0.86 (s, 9H, cis-isomer), 1.65-1.75 (m, 1H, cis-
isomer), 1.89 (br s, OH, 1H, trans-isomer), 1.96 (br s, OH, 1H,
cis-isomer), 2.08-2.16 (m, 2H, cis-isomer), 2.16-2.30 (m, 4H,
trans-isomer), 2.45-2.52 (m, 2H, cis-isomer), 2.56-2.66 (m,
1H, trans-isomer), 7.22-7.41 (m), 7.54-7.59 (m). Anal. Calcd
for C14H20O: C, 82.30; H, 9.87. Found: C, 82.06; H, 10.03.
1-Bu tyl-3-ter t-bu tylcyclobu ta n ol (6c, cis/tr a n s ) 86/14).
1
White solid; H NMR (400 MHz, CDCl3) δ 0.80 (s, 9H, trans-
isomer), 0.86 (s, 9H, cis-isomer), 1.20-1.82 (m), 1.94-2.00 (m,
2H, cis-isomer), 2.35-2.45 (m, 1H, trans-isomer). Anal. Calcd
for C12H24O: C, 78.20; H, 13.12. Found: C, 78.36; H, 13.27.
1-Meth yl-7-vin ylbicyclo[4.2.0]octa n -7-ol (13). Colorless
1
oil; H NMR (270 MHz, CDCl3) δ 1.09 (s, 3H), 1.14-1.70 (m,
8H), 1.87 (d, J ) 12.6 Hz, 1H), 1.89-1.97 (m, 1H), 1.98 (d, J
) 12.6 Hz, 1H), 2.03 (br dd, J ) 7.4, 3.1 Hz, 1H), 4.98 (dd, J
) 10.6, 1.4 Hz, 1H), 5.14 (dd, J ) 17.3, 1.4 Hz, 1H), 5.99 (dd,
J ) 17.3, 10.6 Hz, 1H); 13C NMR (67.8 MHz, CDCl3) δ 20.2,
21.2, 22.6, 28.4, 31.7, 36.0, 47.3, 47.9, 75.7, 110.8, 145.6. Anal.
Calcd for C11H18O: C, 79.47; H, 10.91. Found: C, 79.39; H,
10.77.
1-P h en yl-6-vin ylbicyclo[3.2.0]h ep ta n -6-ol (14). White
solid; mp 51.4-52.2 °C; 1H NMR (270 MHz, CDCl3) δ 1.53 (td,
J ) 12.4, 6.9 Hz, 1H), 1.63 (s, OH, 1H), 1.70-2.15 (m, 5H),
2.18 (d, J ) 12.8 Hz, 1H), 2.71 (dd, J ) 12.8, 2.9 Hz, 1H), 2.94
(br dd, J ) 8.0, 2.9 Hz, 1H), 4.87 (dd, J ) 10.7, 1.1 Hz, 1H),
5.06 (dd, J ) 17.3, 1.1 Hz, 1H), 5.94 (dd, J ) 17.3, 10.7 Hz,
1H), 7.14-7.34 (m, 5H); 13C NMR (67.8 MHz, CDCl3) δ 27.5,
27.5, 44.4, 45.2, 46.2, 54.4, 69.8, 109.7, 125.4, 125.8, 128.2,
145.2, 148.5. Anal. Calcd for C15H18O: C, 84.07; H, 8.47.
Found: C, 83.79; H, 8.63.
1-P h en yl-7-vin ylbicyclo[4.2.0]octan -7-ol (15). White solid;
mp 55.7-56.1 °C; 1H NMR (400 MHz, CDCl3) δ 1.13-1.30 (m,
1H), 1.45-1.53 (m, 1H), 1.66 (s, OH, 1H), 1.67-1.85 (m, 3H),
1.87 (br d, J ) 11.7 Hz, 2H), 2.34 (td, J ) 13.2, 3.4 Hz, 1H),
2.37 (d, J ) 12.2 Hz, 1H), 2.41 (d, J ) 12.2 Hz, 1H), 2.69 (br
d, J ) 6.8 Hz, 1H), 4.96 (d, J ) 10.8 Hz, 1H), 5.13 (d, J ) 17.1
Hz, 1H), 5.90 (dd, J ) 17.1, 10.8 Hz, 1H), 7.14-7.20 (m, 3H),
7.27-7.33 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 20.4, 21.5,
23.0, 38.6, 40.4, 45.2, 48.4, 76.6, 111.1, 125.2, 125.8, 128.0,
144.9, 152.3. Anal. Calcd for C16H20O: C, 84.16; H, 8.83.
Found: C, 84.41; H, 9.06.
2-P h en ylspir o[3.5]n on an -2-ol (31). White solid; mp 101.7-
1
102.2 °C; H NMR (400 MHz, CDCl3) δ 1.32-1.74 (m, 10H),
1.84 (br s, OH, 1H), 2.17 (d, J ) 13.7 Hz, 2H), 2.40 (d, J )
13.7 Hz, 2H), 7.23-7.28 (m, 1H), 7.33-7.38 (m, 2H), 7.42-
7.47 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 22.9, 23.1, 25.9,
31.4, 38.6, 39.2, 47.1, 73.0, 125.1, 127.0, 128.4, 147.8. Anal.
Calcd for C15H20O: C, 83.29; H, 9.32. Found: C, 83.01; H, 9.11.
1
2-Bu tylsp ir o[3.5]n on a n -2-ol (32). Colorless oil; H NMR
(400 MHz, CDCl3) δ 0.92 (t, J ) 7.3 Hz, 3H), 1.25-1.43 (m,
13H), 1.50-1.57 (m, 4H), 1.73 (d, J ) 13.2 Hz, 2H), 1.86 (d, J
) 13.2 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 14.1, 22.8, 23.0,
23.1, 25.3, 25.8, 30.5, 38.8, 40.2, 43.2, 46.5, 71.4. Anal. Calcd
for C13H24O: C, 79.53; H, 12.32. Found: C, 79.77; H, 12.59.
3,3-Dibu tyl-1-p h en ylcyclobu ta n ol (33). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 0.84 (t, J ) 7.3 Hz, 3H), 0.94 (t, J
) 7.3 Hz, 3H), 1.05-1.40 (m, 10H), 1.63-1.70 (m, 2H), 1.75
(br s, OH, 1H), 2.16 (d, J ) 13.7 Hz, 2H), 2.39 (d, J ) 13.7 Hz,
2H), 7.23-7.28 (m, 1H), 7.34-7.39 (m, 2H), 7.42-7.46 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 14.1, 14.2, 23.2, 23.4, 26.2, 26.3,
32.9, 38.0, 38.6, 46.7, 72.9, 125.1, 127.0, 128.4, 147.9. Anal.
Calcd for C18H28O: C, 83.02; H, 10.84. Found: C, 82.74; H,
10.92.
1-Meth yl-7-p h en ylbicyclo[4.2.0]octa n -7-ol (19). Color-
1
less oil; H NMR (400 MHz, CDCl3) δ 1.10 (s, 3H), 1.21-1.32
(m, 1H), 1.48-1.77 (m, 5H), 1.75 (s, OH, 1H), 1.82-1.91 (m,
1H), 1.96-2.06 (m, 1H), 2.15 (d, J ) 12.0 Hz, 1H), 2.29 (d, J
) 12.0 Hz, 1H), 2.38 (br dd, J ) 7.8, 2.4 Hz, 1H), 7.21-7.25
(m, 1H), 7.30-7.40 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 21.1,
21.4, 22.8, 28.3, 31.6, 35.9, 48.1, 48.7, 76.7, 124.8, 126.9, 128.4,
148.4. Anal. Calcd for C15H20O: C, 83.29; H, 9.32. Found: C,
83.25; H, 9.24.
1,3,3-Tr ibu tylcyclobu ta n ol (34). Colorless oil; 1H NMR
(400 MHz, CDCl3) δ 0.90 (t, J ) 7.3 Hz, 3H), 0.90 (t, J ) 7.3
Hz, 3H), 0.92 (t, J ) 7.3 Hz, 3H), 1.05-1.36 (m, 14H), 1.47-
1.57 (m, 5H), 1.73 (d, J ) 13.2 Hz, 2H), 1.83 (d, J ) 13.2 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 14.2, 14.2, 23.0, 23.4, 25.3,
26.1, 26.4, 32.2, 38.5, 39.5, 43.3, 46.1, 71.3. Anal. Calcd for
C
16H32O: C, 79.93; H, 13.41. Found: C, 79.65; H, 13.38.
7-(4-Ch lor oph en yl)-1-m eth ylbicyclo[4.2.0]octan -7-ol (21).
Colorless oil; 1H NMR (400 MHz, CDCl3) δ 1.11 (s, 3H), 1.19-
1.32 (m, 1H), 1.46-1.75 (m, 6H), 1.78-1.86 (m, 1H), 1.93-
2.04 (m, 1H), 2.14 (d, J ) 12.2 Hz, 1H), 2.26 (d, J ) 12.2 Hz,
1,3,3-Tr ip h en ylcyclobu ta n ol (35). White solid; mp 130.7-
131.6 °C; 1H NMR (400 MHz, CDCl3) δ 1.98 (s, OH, 1H), 3.32
(dm, J ) 8.5 Hz, 2H), 3.47 (dm, J ) 8.5 Hz, 2H), 7.05-7.10
(m, 1H), 7.14-7.39 (m, 12H), 7.45-7.49 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 44.0, 49.9, 73.4, 125.0, 125.6, 125.7, 126.1,
126.4, 127.2, 128.3, 128.3, 128.5, 146.0, 149.3, 149.5. Anal.
Calcd for C22H20O: C, 87.96; H, 6.71. Found: C, 84.74; H, 6.77.
3-Meth yl-1,3-d ip h en ylcyclobu ta n ol (36, cis a n d tr a n s
m ixtu r e). White solid; 1H NMR (400 MHz, CDCl3) δ 1.27 (s),
1.69 (br s, OH), 1.72 (s), 2.96 (d, J ) 12.7 Hz), 2.86-3.03 (m),
7.10-7.44 (m), 7.54-7.58 (m). Anal. Calcd for C17H18O: C,
85.67; H, 7.61. Found: C, 85.39; H, 7.65.
1H), 2.32 (br dd, J ) 7.8, 2.9 Hz, 1H), 7.28-7.35 (m, 4H); 13
C
NMR (100 MHz, CDCl3) δ 21.0, 21.3, 22.8, 28.3, 31.6, 35.9,
48.2, 48.8, 76.6, 126.4, 128.4, 132.6, 146.8. Anal. Calcd for
C
15H19ClO: C, 71.85; H, 7.64. Found: C, 71.86; H, 7.87.
7-(3-Ch lor oph en yl)-1-m eth ylbicyclo[4.2.0]octan -7-ol (22).
Colorless oil; 1H NMR (400 MHz, CDCl3) δ 1.12 (s, 3H), 1.20-
1.32 (m, 1H), 1.50-1.72 (m, 5H), 1.76 (br s, OH, 1H), 1.78-
1.86 (m, 1H), 1.94-2.03 (m, 1H), 2.13 (d, J ) 12.2 Hz, 1H),
2.26 (d, J ) 12.2 Hz, 1H), 2.33 (br dd, J ) 7.3, 2.9 Hz, 1H),
7.18-7.28 (m, 3H), 7.37 (s, 1H); 13C NMR (100 MHz, CDCl3) δ
2,8,8-Tr im et h yl-4-p h en ylt r icyclo[5.1.1.02,5]n on a n -4-ol
(43). The stereochemistry of 43 was confirmed by the observa-

Oxidative Transformation of tert-Cyclobutanols
J . Org. Chem., Vol. 66, No. 4, 2001 1463
tion of the NOE spectra (methyl protons; δ 0.92, 1.15, 1.28
ppm and methine proton; δ 2.71 ppm). Colorless oil; 1H NMR
(400 MHz, CDCl3) δ 0.92 (s, 3H), 1.15 (s, 3H), 1.28 (s, 3H),
1.64 (br s, OH, 1H), 1.71 (dd, J ) 6.3, 4.9 Hz, 1H), 1.88-2.01
(m, 2H), 2.05 (d, J ) 10.7 Hz, 1H), 2.24 (dddd, J ) 10.7, 6.3,
6.3, 2.0 Hz, 1H), 2.31 (ddd, J ) 13.7, 2.9, 2.4 Hz, 1H), 2.41
(dd, J ) 13.7, 1.7 Hz, 1H), 2.53 (d, J ) 13.7 Hz, 1H), 2.71 (br
d, J ) 10.7 Hz, 1H), 7.24-7.29 (m, 1H), 7.37 (t, J ) 7.3 Hz,
2H), 7.49 (d, J ) 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
24.0, 24.0, 27.2, 27.5, 28.6, 34.9, 39.8, 41.0, 45.3, 46.7, 50.2,
71.3, 125.1, 127.0, 128.5, 149.8. Anal. Calcd for C18H24O: C,
84.32; H, 9.43. Found: C, 84.54; H, 9.69.
Typ ica l P r oced u r e for P a lla d iu m (II)-Ca ta lyzed Tr a n s-
for m a tion of ter t-Cyclobu ta n ols u n d er Oxygen Atm o-
sp h er e. To a mixture of Pd(OAc)2 (0.05 mmol) and toluene (3
mL) in a 10-mL two-necked flask fitted with an O2 balloon
were added pyridine (1.0 mmol) and MS3A (powder, 50 mg)
activated by calcination. After oxygen was introduced into the
vessel and the mixture was stirred at 80 °C for 5 min, alcohol
(0.5 mmol) in toluene (2 mL) was added. In some cases, ethyl
acrylate (0.1-0.5 mmol) was added before the addition of
alcohol. The mixture was stirred at 80 °C under O2 until the
reaction had reached completion by monitoring with TLC
analysis. The reaction mixture was cooled to room temperature
and then filtered through a pad of Florisil. The filtrate was
concentrated under vacuum to give a yellow oil that was
subjected to column chromatography on SiO2 with EtOAc-
hexane (2/98) as eluents.
1H), 4.89 (s, 1H), 7.41-7.47 (m, 2H), 7.50-7.56 (m, 1H), 7.90-
7.96 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 27.5 (t), 28.7 (t),
29.6 (t), 30.8 (t), 35.4 (t), 52.7 (d), 114.6 (t), 128.5 (d), 132.6
(d), 136.8 (s), 149.5 (s), 201.2 (s). Anal. Calcd for C15H18O: C,
84.07; H, 8.47. Found: C, 83.90; H, 8.52.
Bu tyl 2-Meth ylen e-1-cycloh ep tyl Keton e (8c). Colorless
oil; IR (neat) 2927, 2855, 1711 (CdO), 1635, 1451, 894 cm-1
;
1H NMR (400 MHz, CDCl3) δ 0.89 (t, J ) 7.3 Hz, 3H), 1.18-
1.38 (m, 4H), 1.52 (qui, J ) 7.3 Hz, 2H), 1.65-1.90 (m, 6H),
2.11 (td, J ) 10.3, 3.4 Hz, 1H), 2.24-2.34 (m, 1H), 2.40 (dt, J
) 17.1, 7.3 Hz, 1H), 2.55 (dt, J ) 17.1, 7.3 Hz, 1H), 3.32 (dd,
J ) 10.3, 5.4 Hz, 1H), 4.82 (s, 1H), 4.94 (s, 1H); 13C NMR (100
MHz, CDCl3) δ 13.9 (q), 22.3 (t), 26.0 (t), 26.6 (t), 28.9 (t), 29.9
(t), 30.7 (t), 34.5 (t), 40.5 (t), 59.2 (d), 114.8 (t), 149.4 (s), 211.3
(s). Anal. Calcd for C13H22O: C, 80.36; H, 11.41. Found: C,
80.11; H, 11.61.
3-Meth ylen ebicyclo[2.2.1]h ep t-exo-2-yl P h en yl Keton e
(9b). Colorless oil; IR (neat) 2961, 2923, 2871, 1683 (CdO),
1655, 1448, 1337, 1237, 1206, 876, 766, 694 cm-1 1H NMR
;
(270 MHz, CDCl3) δ 1.31 (dm, J ) 9.9 Hz, 1H), 1.42-1.50 (m,
2H), 1.68-1.77 (m, 2H), 1.85 (dm, J ) 9.9 Hz, 1H), 2.65 (s,
1H), 2.79 (s, 1H), 3.89 (d, J ) 1.9 Hz, 1H), 4.50 (d, J ) 2.1 Hz,
1H), 5.02 (d, J ) 2.1 Hz, 1H), 7.43-7.60 (m, 3H), 7.96-8.01
(m, 2H); 13C NMR (67.8 MHz, CDCl3) δ 28.7 (t), 29.6 (t), 37.1
(t), 41.7 (d), 45.5 (d), 55.1 (d), 105.5 (t), 128.6 (d), 128.8 (d),
132.8 (d), 137.6 (s), 153.5 (s), 199.1 (s). Anal. Calcd for
C
15H16O: C, 84.87; H, 7.60. Found: C, 85.11; H, 7.69.
Bu tyl 3-Meth ylen ebicyclo[2.2.1]h ep t-exo-2-yl Keton e
2-Meth ylen e-1-cycloh exyl Vin yl Keton e (7a ). Colorless
oil; IR (neat) 2935, 2858, 1698 (CdO), 1678, 1645, 1612, 1447,
1400, 979, 962, 898 cm-1; 1H NMR (270 MHz, CDCl3) δ 1.43-
1.80 (m, 5H), 1.92-2.04 (m, 1H), 2.18 (dd, J ) 5.9, 5.9 Hz,
2H), 3.35 (dd, J ) 6.7, 4.3 Hz, 1H), 4.63 (d, J ) 1.1 Hz, 1H),
4.87 (d, J ) 1.1 Hz, 1H), 5.69 (dd, J ) 10.4, 1.7 Hz, 1H), 6.28
(dd, J ) 17.5, 1.7 Hz, 1H), 6.58 (dd, J ) 17.5, 10.4 Hz, 1H);
13C NMR (67.8 MHz, CDCl3) δ 23.7 (t), 28.1 (t), 28.9 (t), 35.0
(t), 54.7 (d), 110.4 (t), 127.7 (t), 134.7 (d), 147.5 (s), 200.8 (s).
Anal. Calcd for C10H14O: C, 79.96; H, 9.39. Found: C, 79.70;
H, 9.56.
2-Meth ylen e-1-cycloh exyl P h en yl Keton e (7b). Color-
less oil; IR (neat) 2934, 2857, 1685 (CdO), 1644, 1597, 1447,
1360, 1247, 1199, 953, 894, 752, 692 cm-1; 1H NMR (270 MHz,
CDCl3) δ 1.45-2.03 (m, 6H), 2.15-2.33 (m, 1H), 2.42 (ddd, J
) 12.6, 4.2, 4.2 Hz, 1H), 3.99 (br dd, J ) 8.7, 4.2 Hz, 1H), 4.44
(s, 1H), 4.80 (s, 1H), 7.40-7.55 (m, 3H), 7.92-7.97 (m, 2H);
13C NMR (67.8 MHz, CDCl3) δ 24.6 (t), 28.3 (t), 30.1 (t), 35.9
(t), 51.5 (d), 109.9 (t), 128.5 (d), 132.8 (d), 137.1 (s), 148.8 (s),
201.8 (s). Anal. Calcd for C14H16O: C, 83.96; H, 8.05. Found:
C, 84.23; H, 8.15.
(9c). Colorless oil; IR (neat) 2959, 2872, 1712 (CdO), 1655,
1454, 883 cm-1; 1H NMR (400 MHz, CDCl3) δ 0.91 (t, J ) 7.3
Hz, 3H), 1.22-1.38 (m, 5H), 1.52-1.72 (m, 5H), 2.51 (t, J )
7.3 Hz, 2H), 2.57 (br s, 1H), 2.73 (br s, 1H), 3.02 (br d, J ) 2.0
Hz, 1H), 4.71 (d, J ) 1.7 Hz, 1H), 5.02 (d, J ) 1.7 Hz, 1H); 13
C
NMR (100 MHz, CDCl3) δ 13.9 (q), 22.4 (t), 26.0 (t), 28.4 (t),
30.0 (t), 37.2 (t), 40.8 (d), 42.0 (t), 45.3 (d), 60.8 (d), 104.8 (t),
153.4 (s), 209.7 (s). Anal. Calcd for C13H20O: C, 81.20; H, 10.48.
Found: C, 81.49; H, 10.65.
3-Meth ylin d en -2-yl P h en yl Keton e (10b). Colorless oil;
IR (neat) 1633 (CdO), 1597, 1577, 1446, 1382, 1353, 1261, 935,
915, 762, 724, 700 cm-1; 1H NMR (400 MHz, CDCl3) δ 2.15 (t,
J ) 2.4 Hz, 3H), 3.83 (q, J ) 2.4 Hz, 2H), 7.33-7.57 (m, 7H),
7.76 (d, J ) 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 13.4
(q), 40.2 (t), 121.1 (d), 123.9 (d), 126.7 (d), 127.5 (d), 128.4 (d),
128.7 (d), 132.0 (d), 138.8 (s), 140.1 (s), 143.5 (s), 145.4 (s),
147.9 (s), 195.4 (s). Anal. Calcd for C17H14O: C, 87.15; H, 6.02.
Found: C, 86.94; H, 5.95.
Bu tyl 3-Meth ylin d en -2-yl Keton e (10c). White solid; mp
1
57.0-57.5 °C; H NMR (270 MHz, CDCl3) δ 0.95 (t, J ) 7.3
Hz, 3H), 1.32-1.48 (m, 2H), 1.62-1.74 (m, 2H), 2.55 (t, J )
2.3 Hz, 3H), 2.73 (t, J ) 7.3 Hz, 2H), 3.69 (q, J ) 2.3 Hz, 2H),
7.34-7.40 (m, 2H), 7.46-7.54 (m, 2H); 13C NMR (67.8 MHz,
CDCl3) δ 13.0 (q), 14.0 (q), 22.5 (t), 26.2 (t), 39.0 (t), 41.9 (t),
121.5 (d), 124.0 (d), 126.8 (d), 127.9 (d), 137.4 (s), 143.0 (s),
145.6 (s), 149.8 (s), 199.5 (s). Anal. Calcd for C15H18O: C, 84.07;
H, 8.47. Found: C, 83.53; H, 8.52.
Bu tyl 2-Meth ylen e-1-cycloh exyl Keton e (7c). Colorless
oil; IR (neat) 2934, 2859, 1712 (CdO), 1644, 1447, 1051, 893
1
cm-1; H NMR (400 MHz, CDCl3) δ 0.90 (t, J ) 7.4 Hz, 1H),
1.30 (sxt, J ) 7.4 Hz, 2H), 1.42-1.72 (m, 9H), 1.96-2.06 (m,
1H), 2.08-2.21 (m, 2H), 2.46 (dt, J ) 16.6, 7.4 Hz, 1H), 2.49
(dt, J ) 16.6, 7.4 Hz, 1H), 3.18 (t, J ) 5.1 Hz, 1H), 4.66 (s,
1H), 4.85 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 13.9 (q), 22.4
(t), 23.4 (t), 25.9 (t), 28.0 (t), 28.8 (t), 34.6 (t), 40.8 (t), 56.4 (d),
110.2 (t), 147.9 (s), 211.9 (s). Anal. Calcd for C12H20O: C, 79.94;
H, 11.18. Found: C, 80.06; H, 11.36.
(E)-3-Meth yl-1-p h en yl-2-n on en -1-on e (11b). Colorless
oil; IR (neat) 2956, 2929, 2857, 1661 (CdO), 1611, 1448, 1239,
1
700 cm-1; H NMR (400 MHz, CDCl3) δ 0.90 (t, J ) 6.8 Hz,
3H), 1.25-1.40 (m, 6H), 1.50-1.60 (m, 2H), 2.19 (d, J ) 1.5
Hz, 3H), 2.25 (t, J ) 7.3 Hz, 2H), 6.73 (q, J ) 1.5 Hz, 1H),
7.41-7.55 (m, 3H), 7.89-7.95 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 14.1 (q), 19.8 (q), 22.6 (t), 27.6 (t), 29.0 (t), 31.7 (t),
41.6 (t), 120.5 (d), 128.2 (d), 128.4 (d), 132.2 (d), 139.5 (s), 160.6
(s), 191.8 (s). Anal. Calcd for C16H22O: C, 83.43; H, 9.63.
Found: C, 83.51; H, 9.80.
2-Meth ylen e-1-cycloh ep tyl Vin yl Keton e (8a ). Colorless
oil; IR (neat) 2927, 2854, 1697 (CdO), 1677, 1635, 1447, 1399,
1
983, 962, 893 cm-1; H NMR (400 MHz, CDCl3) δ 1.22-1.40
(m, 3H), 1.62-1.92 (m, 5H), 2.17 (ddd, J ) 13.6, 9.8, 3.9 Hz,
1H), 2.34 (ddd, J ) 13.6, 12.8, 3.9 Hz, 1H), 3.51 (dd, J ) 10.5,
5.1 Hz, 1H), 4.80 (s, 1H), 4.97 (s, 1H), 5.69 (dd, J ) 10.7, 1.5
Hz, 1H), 6.26 (dd, J ) 17.6, 1.5 Hz, 1H), 6.48 (dd, J ) 17.6,
10.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 26.9 (t), 29.0 (t),
29.5 (t), 30.2 (t), 34.9 (t), 56.8 (d), 115.3 (t), 127.7 (t), 134.9 (d),
148.8 (s), 200.1 (s). Anal. Calcd for C11H16O: C, 80.44; H, 9.82.
Found: C, 80.25; H, 9.84.
2-Hexyl-1-octen -4-on e a n d (E)-7-Meth yl-6-tr id ecen -5-
1
on e (11c, â,γ/r,â ) 34/66). Colorless oil; H NMR (400 MHz,
CDCl3) δ 0.85-0.94 (m), 1.22-1.64 (m), 2.02 (t, J ) 7.3 Hz,
2H, â,γ), 2.11 (t, J ) 7.8 Hz, 2H, R,â), 2.12 (s, 3H, R,â), 2.41 (t,
J ) 7.8 Hz, 2H, R,â), 2.45 (t, J ) 7.3 Hz, 2H, â,γ), 3.10 (s, 2H,
â,γ), 4.83 (s, 1H, â,γ), 4.93 (s, 1H, â,γ), 6.05 (s, 1H, R,â). Anal.
Calcd for C14H26O: C, 79.94; H, 12.46. Found: C, 79.88; H,
12.73.
2-Meth ylen e-1-cycloh ep tyl P h en yl Keton e (8b). Color-
less oil; IR (neat) 2926, 2853, 1681 (CdO), 1447, 1210, 692
cm-1; 1H NMR (400 MHz, CDCl3) δ 1.35-1.55 (m, 3H), 1.70-
2.05 (m, 5H), 2.37 (ddd, J ) 14.0, 9.8, 4.4 Hz, 1H), 2.46 (dt, J
) 14.0, 4.9 Hz, 1H), 4.15 (dd, J ) 10.7, 4.9 Hz, 1H), 4.72 (s,
3-ter t-Bu tyl-1-p h en yl-3-bu ten -1-on e a n d (E)-3,4,4-Tr i-
m eth yl-1-p h en yl-2-p en ten -1-on e (12b, â,γ/r,â ) 56/44).

1464 J . Org. Chem., Vol. 66, No. 4, 2001
Nishimura et al.
1
Colorless oil; H NMR (400 MHz, CDCl3) δ 1.13 (s, 9H; â,γ),
Hz, 1H), 2.68 (d, J ) 16.6 Hz, 1H), 2.95 (d, J ) 16.6 Hz, 1H),
7.20 (s, 1H), 7.25 (d, J ) 8.3 Hz, 1H), 7.92 (d, J ) 8.3 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 17.2 (q), 21.0 (t), 21.2 (t), 25.7
(t), 37.6 (s), 41.0 (t), 46.0 (t), 54.9 (d), 126.9 (d), 128.4 (d), 129.1
(d), 130.9 (s), 139.4 (s), 143.4 (s), 198.7 (s). Anal. Calcd for
1.20 (s, 9H; R,â), 2.16 (d, J ) 1.0 Hz, 3H; R,â), 3.70 (s, 2H;
â,γ), 4.67 (s, 1H; â,γ), 5.08 (s, 1H; â,γ), 6.76 (d, J ) 1.0 Hz,
1H; R,â), 7.40-7.56 (m), 7.83-8.03 (m). Anal. Calcd for
C
14H18O: C, 83.12; H, 8.97. Found: C, 82.84; H, 9.21.
2-ter t-Bu tyl-1-octen -4-on e a n d (E)-2,3,3-Tr im eth yl-3-
C
15H17ClO: C, 72.43; H, 6.89. Found: C, 72.16; H, 6.93.
t r a n s-7-Ch lor o-1,2,3,4,4a ,9a -h e xa h yd r o-4a -m e t h yl-
n on en -5-on e (12c, â,γ/r,â) 71/29). Colorless oil; 1H NMR
(400 MHz, CDCl3) δ 0.90 (t, J ) 7.3 Hz, 3H; â,γ), 0.91 (t, J )
7.3 Hz, 3H; R,â), 1.06 (s, 9H; â,γ), 1.11 (s, 9H; R,â), 1.24-1.38
(m), 1.50-1.64 (m), 2.12 (d, J ) 1.0 Hz, 3H; R,â), 2.44 (t, J )
7.3 Hz, 2H; R,â), 2.47 (t, J ) 7.3 Hz, 2H; â,γ), 3.13 (s, 2H; â,γ),
4.72 (s, 1H; â,γ), 5.07 (s, 1H; â,γ), 6.12 (s, 1H; R,â). Anal. Calcd
for C12H22O: C, 79.06; H, 12.16. Found: C, 79.31; H, 12.36.
1-Met h yl-8-m et h ylen eb icyclo[4.3.0]n on a n -7-on e (16).
Colorless oil; IR (neat) 2929, 2860, 1727 (CdO), 1643, 1641,
1448, 1057, 949, 934 cm-1; 1H NMR (400 MHz, CDCl3) δ 1.02-
1.27 (m, 2H), 1.19 (s, 3H), 1.32-1.58 (m, 5H), 1.95-2.02 (m,
2H), 2.33 (dt, J ) 16.1, 3.1 Hz, 1H), 2.45 (dt, J ) 16.1, 1.6 Hz,
1H), 5.30-5.33 (m, 1H), 6.05-6.08 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 21.2 (t), 21.6 (t), 22.6 (t), 25.2 (q), 34.6 (t), 35.8
(s), 43.0 (t), 55.8 (d), 117.9 (t), 144.4 (s), 207.3 (s). Anal. Calcd
for C11H16O: C, 80.44; H, 9.82. Found: C, 80.25; H, 9.96.
7-Meth ylen e-1-ph en ylbicyclo[3.3.0]octan -6-on e (17). Col-
orless oil; IR (neat) 2955, 2909, 2875, 1723 (CdO), 1642, 1497,
9(10H)-a n th r a cen on e (27). White solid; mp 123.5-123.7 °C;
IR (KBr) 2922, 2854, 1683 (CdO), 1592, 1473, 1446, 1409,
1250, 822, 690 cm-1;1H NMR (400 MHz, CDCl3) δ 0.84 (s, 3H),
1.22-1.68 (m, 6H), 1.87-1.95 (m, 1H), 2.07-2.14 (m, 1H), 2.36
(dd, J ) 11.5, 3.7 Hz, 1H), 2.70 (d, J ) 16.4 Hz, 1H), 2.92 (d,
J ) 16.4 Hz, 1H), 7.15 (d, J ) 7.8 Hz, 1H), 7.41 (dd, J ) 7.8,
2.5 Hz, 1H), 7.94 (d, J ) 2.5 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 17.2 (q), 21.1 (t), 21.2 (t), 25.7 (t), 37.6 (s), 41.0 (t),
45.7 (t), 54.9 (d), 126.5 (d), 130.9 (d), 132.6 (s), 133.1 (d), 133.8
(s), 140.0 (s), 198.5 (s). Anal. Calcd for C15H17ClO: C, 72.43;
H, 6.89. Found: C, 72.30; H, 6.90.
tr a n s-1,2,3,4,4a ,9a -H exa h yd r o-6-m et h oxy-4a -m et h yl-
9(10H)-a n th r a cen on e (28). White solid; mp 84.7-85.0 °C;
IR (KBr) 2928, 1677 (CdO), 1600, 1445, 1329, 1278, 1253,
1105, 1094, 1028 cm-1;1H NMR (400 MHz, CDCl3) δ 0.84 (s,
3H), 1.20-1.62 (m, 6H), 1.82-1.93 (m, 1H), 2.07-2.15 (m, 1H),
2.31 (dd, J ) 11.5, 3.7 Hz, 1H), 2.65 (d, J ) 16.1 Hz, 1H), 2.93
(d, J ) 16.1 Hz, 1H), 3.84 (s, 3H), 6.65 (d, J ) 2.4 Hz, 1H),
6.79 (dd, J ) 8.8, 2.4 Hz, 1H), 7.95 (d, J ) 8.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 17.2 (q), 21.2 (t), 21.3 (t), 25.9 (t),
37.5 (s), 41.1 (t), 46.7 (t), 54.8 (d), 55.3 (q), 112.5 (d), 113.3 (d),
126.2 (s), 129.1 (d), 144.2 (s), 163.5 (s), 198.4 (s). Anal. Calcd
for C16H20O2: C, 78.65; H, 8.25. Found: C, 78.51; H, 8.18.
1446, 1273, 1088, 938, 761, 701 cm-1 1H NMR (400 MHz,
;
CDCl3) δ 1.56-1.74 (m, 3H), 1.97-2.24 (m, 3H), 2.85 (dt, J )
16.6, 2.9 Hz, 1H), 3.01 (br dd, J ) 10.0, 2.7 Hz, 1H), 3.10 (dt,
J ) 16.6, 2.0 Hz, 1H), 5.36-5.39 (m, 1H), 6.06-6.11 (m, 1H),
7.21-7.28 (m, 3H), 7.31-7.36 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 24.4 (t), 29.1 (t), 40.4 (t), 41.5 (t), 53.2 (s), 58.0 (d),
118.9 (t), 125.7 (d), 126.3 (d), 128.5 (d), 144.2 (s), 147.5 (s),
209.5 (s). Anal. Calcd for C15H16O: C, 84.87; H, 7.60. Found:
C, 85.14; H, 7.68.
4-Meth oxyp h en yl Sp ir o[2.5]oct-4-yl Keton e (28′). Color-
less oil; IR (neat) 2950, 1669 (CdO), 1600, 1250, 1209, 1173
cm-1; 1H NMR (400 MHz, CDCl3) δ 0.15-0.28 (m, 3H), 0.40-
0.46 (m, 1H), 1.38-1.96 (m, 8H), 3.26 (dd, J ) 7.6, 4.2 Hz,
1H), 3.86 (s, 3H), 6.92 (d, J ) 9.0 Hz, 2H), 7.89 (d, J ) 9.0 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 9.5 (t), 12.1 (t), 20.7 (s),
24.1 (t), 25.3 (t), 28.6 (t), 35.8 (t), 48.4 (d), 55.4 (q), 113.6 (d),
130.5 (d), 130.8 (s), 163.2 (s), 201.0 (s). Anal. Calcd for
8-Meth ylen e-1-p h en ylbicyclo[4.3.0]h ep ta n -7-on e (18).
Colorless oil; IR (neat) 2934, 2857, 1727 (CdO), 1644, 1046,
1
933, 764, 701 cm-1; H NMR (400 MHz, CDCl3) δ 1.03-1.19
(m, 2H), 1.35-1.54 (m, 3H), 1.67-1.76 (m, 1H), 2.05-2.12 (m,
1H), 2.27-2.34 (m, 1H), 2.57 (dt, J ) 16.6, 3.2 Hz, 1H), 2.82
(dt, J ) 16.6, 1.5 Hz, 1H), 2.88 (dt, J ) 5.4, 2.7 Hz, 1H), 5.35-
5.38 (m, 1H), 6.13-6.16 (m, 1H), 7.22-7.27 (m, 2H), 7.34-
7.42 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 21.6 (t), 21.8 (t),
22.3 (t), 35.4 (t), 43.9 (s), 44.9 (t), 52.9 (d), 118.2 (t), 126.2 (d),
128.6 (d), 143.5 (s), 146.0 (s), 206.2 (s). Anal. Calcd for
C
16H20O2: C, 78.65; H, 8.25. Found: C, 78.65; H, 8.34.
tr a n s-1,2,3,4,4a ,9a -H exa h yd r o-7-m et h oxy-4a -m et h yl-
9(10H)-a n th r a cen on e (29). White solid; mp 86.0-86.3 °C;
IR (KBr) 2919, 2838, 1674 (CdO), 1612, 1498, 1431, 1294,
1271, 1234, 1035, 816, 741 cm-1;1H NMR (400 MHz, CDCl3) δ
0.84 (s, 3H), 1.21-1.68 (m, 6H), 1.87-1.95 (m, 1H), 2.06-2.15
(m, 1H), 2.35 (dd, J ) 11.7, 3.4 Hz, 1H), 2.66 (d, J ) 16.1 Hz,
1H), 2.91 (d, J ) 16.1 Hz, 1H), 3.83 (s, 3H), 7.04 (dd, J ) 8.3,
2.9 Hz, 1H), 7.11 (d, J ) 8.3 Hz, 1H), 7.48 (d, J ) 2.9 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 17.2 (q), 21.2 (t), 21.3 (t), 25.8
(t), 37.8 (s), 41.1 (t), 45.6 (t), 54.9 (d), 55.4 (q), 109.0 (d), 121.3
(d), 130.4 (d), 133.3 (s), 134.2 (s), 158.2 (s), 199.7 (s). Anal.
Calcd for C16H20O2: C, 78.65; H, 8.25. Found: C, 78.53; H,
8.29.
tr a n s-1,2,3,4,4a,12a-Hexah ydr o-4a-m eth yl-12(5H)-n aph -
th a cen on e (30). White solid; mp 195.2-196.2 °C; IR (KBr)
2936, 2859, 1678 (CdO), 1625, 1592, 1445, 1197, 925, 760, 478
cm-1;1H NMR (400 MHz, CDCl3) δ 0.85 (s, 3H), 1.23-1.36 (m,
1H), 1.39-1.69 (m, 5H), 1.87-1.97 (m, 1H), 2.14-2.23 (m, 1H),
2.42 (dd, J ) 11.7, 3.4 Hz, 1H), 2.89 (d, J ) 16.1 Hz, 1H), 3.08
(d, J ) 16.1 Hz, 1H), 7.44 (t, J ) 7.8 Hz, 1H), 7.52 (t, J ) 7.8
Hz, 1H), 7.62 (s, 1H), 7.76 (d, J ) 7.8 Hz, 1H), 7.93 (d, J ) 7.8
Hz, 1H), 8.56 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 17.4 (q),
21.3 (t), 25.8 (t), 37.3 (s), 41.1 (t), 46.5 (t), 55.6 (d), 125.8 (d),
127.0 (d), 127.4 (d), 128.0 (d), 128.2 (d), 129.9 (d), 130.6 (s),
131.6 (s), 136.0 (s), 137.1 (s), 199.9 (s). Anal. Calcd for
C
16H18O: C, 84.91; H, 8.02. Found: C, 84.70; H, 8.02.
tr a n s-1,2,3,4,4a ,9a -H exa h yd r o-4a -m et h yl-9(10H )-a n -
th r a cen on e (20). White solid; mp 71.7-72.2 °C; IR (KBr)
2928, 2863, 1687 (CdO), 1600, 1455, 1446, 1319, 1275, 1212,
749 cm-1;1H NMR (400 MHz, CDCl3) δ 0.85 (s, 3H), 1.22-1.65
(m, 6H), 1.85-1.94 (m, 1H), 2.05-2.15 (m, 1H), 2.37 (dd, J )
11.7, 3.4 Hz, 1H), 2.72 (d, J ) 16.4 Hz, 1H), 2.98 (d, J ) 16.4
Hz, 1H), 7.19 (d, J ) 7.8 Hz, 1H), 7.27 (dd, J ) 7.8, 7.8 Hz,
1H), 7.45 (ddd, J ) 7.8, 7.8, 1.0 Hz, 1H), 7.98 (dd, J ) 7.8, 1.0
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 17.3 (q), 21.2 (t), 21.3
(t), 25.8 (t), 37.6 (s), 41.1 (t), 46.3 (t), 55.0 (d), 126.4 (d), 126.7
(d), 129.3 (d), 132.6 (s), 133.3 (d), 141.8 (s), 199.8 (s). Anal.
Calcd for C15H18O: C, 84.07; H, 8.47. Found: C, 83.88; H, 8.56.
Data for 20 (a colorless crystal, grown in pentane at -10
°C) was collected on a Rigaku AFC7R diffractometer with a
graphite monochromated Mo KR radiation (λ ) 0.71069 Å) and
a 12 kW rotating anode generator. Crystal data for 20 are as
follows: monoclinic, space group P21/n (#14); a ) 9.099(5), b )
6.640(6), c ) 20.065(4) Å; V ) 1205(1) Å3; â ) 96.16(3)°; Z )
4; Dcalcd ) 1.181 g cm-3; µ(Mo KR) ) 0.72 cm-1; total of 2941
reflections within 2θ ) 55°. The final R value was 0.051 (Rw
) 0.055). The structure was solved by direct methods (SIR92)
and refined by full-matrix least-squares techniques. All atoms
were refined anisotropically.
C
19H20O: C, 86.32; H, 7.63. Found: C, 86.15; H, 7.63.
P h en yl Sp ir o[2.5]oct-1-yl Keton e (37). Colorless oil; IR
The stereochemistry of 26-30 was confirmed by that of 20
and almost the same chemical shift of the angular methyl
proton (δ 0.85 ppm).
(neat) 2924, 2851, 1666 (CdO), 1448, 1397, 1218, 984, 719,
689 cm-1;1H NMR (400 MHz, CDCl3) δ 0.94 (dd, J ) 7.3, 3.9
Hz, 1H), 1.13-1.24 (m, 1H), 1.39-1.68 (m, 10H), 2.50 (dd, J
t r a n s-6-Ch lor o-1,2,3,4,4a ,9a -h e xa h yd r o-4a -m e t h yl-
9(10H)-a n th r a cen on e (26). White solid; mp 105.0-106.2 °C;
) 7.3, 5.4 Hz, 1H), 7.43-7.56 (m, 3H), 7.98-8.04 (m, 2H); 13
C
NMR (100 MHz, CDCl3) δ 21.3 (t), 25.8 (t), 26.0 (t), 26.1 (t),
28.3 (t), 32.0 (d), 35.4 (s), 37.8 (t), 128.0 (d), 128.4 (d), 132.3
(d), 139.0 (s), 198.1 (s). Anal. Calcd for C15H18O: C, 84.07; H,
8.47. Found: C, 84.37; H, 8.77.
IR (KBr) 2936, 1690 (CdO), 1595, 1280, 873, 833 cm-1 1H
;
NMR (400 MHz, CDCl3) δ 0.85 (s, 3H), 1.20-1.66 (m, 6H),
1.88-1.96 (m, 1H), 2.06-2.14 (m, 1H), 2.36 (dd, J ) 11.5, 3.7

Oxidative Transformation of tert-Cyclobutanols
J . Org. Chem., Vol. 66, No. 4, 2001 1465
Bu tyl Sp ir o[2.5]oct-1-yl Keton e (38). Colorless oil; IR
(neat) 2926, 2853, 1694 (CdO), 1445, 1399, 1072 cm-1;1H NMR
(400 MHz, CDCl3) δ 0.78 (dd, J ) 7.3, 3.9 Hz, 1H), 0.92 (t, J
) 7.3 Hz, 3H), 1.16-1.25 (m, 1H), 1.25 (dd, J ) 5.9, 3.9 Hz,
1H), 1.27-1.63 (m, 13H), 1.80 (dd, J ) 7.3, 5.9 Hz, 1H), 2.48-
2.62 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 13.9 (q), 21.7 (t),
22.5 (t), 26.0 (t), 26.1 (t), 26.2 (t), 26.5 (t), 28.0 (t), 34.4 (d),
34.5 (s), 37.8 (t), 44.5 (t), 208.8 (s). Anal. Calcd for C13H22O:
C, 80.36; H, 11.41. Found: C, 80.64; H, 11.66.
2,2-Dibu tylcyclop r op yl P h en yl Keton e (39). Colorless
oil; IR (neat) 2957, 2929, 2871, 1668 (CdO), 1449, 1397, 1217,
693 cm-1;1H NMR (400 MHz, CDCl3) δ 0.78 (t, J ) 7.3 Hz,
3H), 0.94 (t, J ) 7.3 Hz, 3H), 0.95-1.08 (m, 2H), 1.12-1.72
(m, 12H), 2.48 (dd, J ) 7.3, 5.4 Hz, 1H). 7.40-7.55 (m, 3H),
7.93-8.02 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 14.0 (q), 14.1
(q), 21.8 (t), 22.8 (t), 23.0 (t), 28.0 (t), 28.7 (t), 29.1 (t), 31.9 (d),
36.2 (s), 37.3 (t), 128.0 (d), 128.4 (d), 132.3 (d), 139.2 (s), 198.4
(s). Anal. Calcd for C18H26O: C, 83.67; H, 10.14. Found: C,
83.71; H, 10.31.
Bu tyl 2,2-Dibu tylcyclop r op yl Keton e (40). Colorless oil.;
IR (neat) 2957, 2930, 2861, 1697 (CdO), 1466, 1398, 1069
cm-1;1H NMR (400 MHz, CDCl3) δ 0.78 (dd, J ) 7.3, 3.9 Hz,
1H), 0.86 (t, J ) 7.3 Hz, 3H), 0.91 (t, J ) 7.3 Hz, 6H), 1.04-
1.15 (m, 1H), 1.22 (dd, J ) 5.9, 3.9 Hz, 1H), 1.24-1.42 (m,
13H), 1.58 (qui, J ) 7.3 Hz, 2H), 1.79 (dd, J ) 7.3, 5.9 Hz,
1H), 2.53 (t, J ) 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
13.9 (q), 14.1 (q), 21.9 (t), 22.4 (t), 22.9 (t), 22.9 (t), 26.4 (t),
27.4 (t), 28.7 (t), 29.3 (t), 34.3 (d), 35.1 (s), 37.2 (t), 44.6 (t),
208.9 (s). Anal. Calcd for C16H30O: C, 80.61; H, 12.68. Found:
C, 80.78; H, 12.96.
P h en yl 2,2-Dip h en ylcyclop r op yl Keton e (41). White
solid; mp 128.7-129.2 °C; IR (KBr) 1668 (CdO), 1497, 1450,
1383, 1221, 1036, 1012, 740, 719, 698, 690 cm-1;1H NMR (400
MHz, CDCl3) δ 1.77 (dd, J ) 7.8, 4.4 Hz, 1H), 2.56 (dd, J )
6.2, 4.4 Hz, 1H), 3.51 (dd, J ) 7.8, 6.2 Hz, 1H), 7.12-7.34 (m,
10H), 7.43-7.49 (m, 2H), 7.52-7.58 (m, 1H), 7.98-8.04 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 21.3 (t), 33.7 (d), 43.8 (s),
126.6 (d), 127.0 (d), 127.2 (d), 128.1 (d), 128.3 (d), 128.6 (d),
128.6 (d), 130.2 (d), 132.8 (d), 138.7 (s), 139.2 (s), 145.2 (s),
195.5 (s). Anal. Calcd for C22H18O: C, 88.56; H, 6.08. Found:
C, 88.52; H, 6.03.
CDCl3) δ 20.6 (t), 28.6 (q), 33.6 (d), 36.5 (s), 126.7 (d), 128.0
(d), 128.1 (d), 128.5 (d), 128.9 (d), 132.4 (d), 138.8 (s), 140.8
(s), 196.2 (s). Anal. Calcd for C17H16O: C, 86.41; H, 6.82.
Found: C, 86.36; H, 6.78.
tr a n s-2-Meth yl-2-p h en ylcyclop r op yl P h en yl Keton e
(42). The stereochemistry of trans-42 was confirmed by the
observation of different NOE spectra (methine proton; δ 2.91
ppm and methylene proton; δ 1.61 ppm). Colorless oil; IR (neat)
1669 (CdO), 1598, 1448, 1386, 1221, 977, 766, 739, 715, 699,
690 cm-1;1H NMR (400 MHz, CDCl3) δ 1.44 (s, 3H), 1.61 (dd,
J ) 7.8, 4.6 Hz, 1H), 1.88 (dd, J ) 6.4, 4.6 Hz, 1H), 2.91 (dd,
J ) 7.8, 6.4 Hz, 1H), 7.25-7.29 (m, 1H), 7.36-7.40 (m, 4H),
7.44-7.49 (m, 2H), 7.53-7.58 (m, 1H), 7.97-8.01 (m, 2H); 13
C
NMR (100 MHz, CDCl3) δ 18.7 (q), 20.9 (t), 33.6 (s), 34.1 (d),
126.5 (d), 126.6 (d), 128.1 (d), 128.6 (d), 128.7 (d), 132.7 (d),
138.7 (s), 145.8 (s), 197.5 (s). Anal. Calcd for C17H16O: C, 86.41;
H, 6.82. Found: C, 86.13; H, 6.80.
2,7,7-Tr im eth yltr icyclo[4.1.1.02.4]oct-4-yl P h en yl Ke-
ton e (44). The stereochemistry of 44 was confirmed by the
observation of different NOE spectra (methyl proton; δ 1.18,
1.29 and 1.32 ppm). White solid; mp 53.4-55.2 °C; IR (KBr)
2896, 1670 (CdO), 1595, 1455, 1385, 1360, 1265, 1230, 1215,
1020, 985, 920, 684, 616 cm-1;1H NMR (400 MHz, CDCl3) δ
0.90 (d, J ) 4.9 Hz, 1H), 1.16 (d, J ) 8.8 Hz, 1H), 1.18 (s, 3H),
1.29 (s, 3H), 1.32 (s, 3H), 1.62 (d, J ) 4.9 Hz, 1H), 1.79 (ddd,
J ) 8.3, 5.4, 2.9 Hz, 1H), 1.93 (t, J ) 5.4 Hz, 1H), 2.09 (dd, J
) 14.2, 2.9 Hz, 1H), 2.12-2.18 (m, 2H), 7.40-7.52 (m, 3H),
7.92-7.97 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 19.8 (q), 22.7
(q), 26.6 (t), 27.2 (q), 27.2 (t), 28.6 (s), 29.6 (s), 32.0 (t), 40.6
(s), 41.8 (d), 46.5 (d), 128.2 (d), 128.9 (d), 132.0 (d), 138.1 (s),
202.3 (s). Anal. Calcd for C18H22O: C, 84.99; H, 8.72. Found:
C, 84.87; H, 8.91.
4,4,6,6-Tetr a m eth ylbicyclo[3.1.1]h ep t-2-en -3-yl P h en yl
Keton e (45). Colorless oil; IR (neat) 2944, 1644 (CdO), 1597,
1263, 872, 726, 699 cm-1;1H NMR (400 MHz, CDCl3) δ 1.11
(s, 3H), 1.34 (s, 3H), 1.38 (s, 3H), 1.41 (s, 3H), 1.52 (d, J ) 9.3
Hz, 1H), 1.85 (t, J ) 6.0 Hz, 1H), 2.36 (dd, J ) 12.0, 6.0 Hz,
1H), 2.37-2.44 (m, 1H), 6.95 (d, J ) 6.0 Hz, 1H), 7.35-7.50
(m, 3H), 7.56-7.63 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 25.1
(q), 25.2 (q), 27.4 (q), 29.4 (q), 30.5 (t), 41.0 (s), 41.7 (s), 43.4
(d), 56.0 (d), 127.9 (d), 128.9 (d), 131.0 (d), 140.7 (s), 142.1 (s),
154.4 (d), 198.0 (s). Anal. Calcd for C18H22O: C, 84.99; H, 8.72.
Found: C, 85.02; H, 8.68.
cis-2-Meth yl-2-p h en ylcyclop r op yl P h en yl Keton e (42).
The stereochemistry of cis-42 was confirmed by the observation
of different NOE spectra (methine proton; δ 2.91 ppm and
methyl proton; δ 1.65 ppm). Colorless oil; IR (neat) 1673
(CdO), 1598, 1448, 1385, 1239, 1215, 1066, 991, 763, 715, 670,
690, cm-1;1H NMR (400 MHz, CDCl3) δ 1.30 (dd, J ) 7.6, 4,2
Hz, 1H), 1.65 (s, 3H), 2.21 (dd, J ) 5.6, 4.2 Hz, 1H), 2.91 (dd,
J ) 7.6, 5.6 Hz, 1H), 7.10-7.20 (m, 5H), 7.42-7.48 (m, 2H),
7.51-7.56 (m, 1H), 7.91-7.95 (m, 2H); 13C NMR (100 MHz,
Su p p or tin g In for m a tion Ava ila ble: Crystallographic
data including ORTEP drawing of compound 20 (Figure S1).
This material is available free of charge via the Internet at
http://pubs.acs.org.
J O0016475