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Intermolecular Additions and Cycloisomerizations by a Pd-Catalyzed Sequence of an Intramolecular Redox Reaction and an Addition.

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acid. A precipitous drop in yield (to 28 YO)resulted when a
palladium complex with an acceptor ligand like trifurylphosphine was used. When complexes with bidentate ligands like
bis(dipheny1phosphino)butane (dppb) were employed, the
reaction was shut down completely. Replacement of the
methoxy group OR' in 1 a with a siloxy substituent (1b) led
again exclusively to the geminal diacetate product, in this
case 2b. In all the cases examined all the products were
obtained as ( E ) isomers.
[(dba)3Pd2 CHC131 3 , Ph3P
PhCH,, reflux
b: R =
Adjusting oxidation states by intramolecular hydrogen
shifts['- 21 is more efficient and "atom economical" than conventional reduction/oxidation sequences in organic synthesis. Such hydrogen shifts may generate trappable reactive
intermediates, ultimately leading to simple additions.[31This
tits in with our program to enhance atom ec~nomy[~]-that
is, to minimize the number of atoms required in the building
blocks of a reaction sequence and to maximize the use of
processes that require only catalytic amounts of any additional reactants-and to generate macrocycles by cycloiso51 Our previous work suggested that a hymeri~ation.'~.
dridopalladium complex isomerizes acetylenes to allenes.r2a1
We postulated that the latter may undergo a second hydropalladation to form a n-allylpalladium complex, which
could undergo a subsequent addition [Eq. (l)] . This overall
, R'= fBuPh,SI
c : R = q C H z
By Barry M . Trost,* Walter Brieden,
and Karl H . Baringhaus
R' = CH3
a: R =tC,H,.
Intermolecular Additions and Cycloisomerizations
by a Pd-Catalyzed Sequence of an Intramolecular
Redox Reaction and an Addition**
, R'=fBuPh,Si
u , R'=CH,
Reaction (b) exhibits excellent chemoselectivity. Neither
double bonds (1c and ld), nor carbonyl and hydroxyl functions on the R group (1 e) are affected. Compounds 4 and 6,
both derived from ketones, react as smoothly as compounds
1 a-e to give the corresponding geminal diacetates 5 and 7
[Eqs.(c) and (d)]. Remarkably, even compounds with car-
b: R = Me+
process would constitute an internal redox reaction and an
addition. We wish to report the development of such a process whereby propargylic acetates are converted into novel
allylic gem-diacetates.'''
In initial experiments the propargylic acetate 1a was treated with 2.5 mol Yo tris(dibenzy1idenacetone) complex 3 and
35 mol Yo triphenylphosphine in toluene with 5 equivalents
of acetic acid. The resulting geminal diacetate 2 a was isolated in 77% yield exclusively as the ( E ) isomer (proven by
NMR spectroscopy) [Eq.(b)]. Only slightly lower yields
(72 YO)were obtained with as little as 1 equivalent of acetic
Prof. Dr. B. M. Trost, W. Brieden, K. H. Baringhaus
Department of Chemistry, Stanford University
Stanford. CA 94305-5080 (USA)
This research was supported by the National Science Foundation, the
General Medical Sciences Institute of the National Institutes of Health
(NIH) and the Deutsche Forschungsgemeinschaft (stipends for W. B. and
K. H. B. ) The mass spectra were recorded at the Mass Spectrometry
Facility of the University of California at San Francisco, which is sponsored bv the Division of Resources of the NIH.
Angew,. Chpm. Inr. Ed. Engl. 1992, 31, N o . 10
; OSifBuMe,
A c
boxyl groups react analogously when 13 equivalents of
acetic acid are used to suppress the intramolecular reaction
with the acid function. Mixed geminal carboxylates such as
8 are also available [Eq.(e)].
OAc 0
Gratifyingly, this new sequence consisting of an intramolecular redox reaction and an addition may be performed intramolecularly in relatively concentrated solutions to gener-
0 VCH Verlagsgesellschafl mbH. W-6940 Weinheim, 1992
0570-0833/92/1010-1335 3 3.50+.255/0
ate macrocycles [Eq.(f)]. For example, a 0.01 M solution of
carboxylic acid 9 in benzene was heated at reflux with 35 mol % 3 and 30 mol% triphenylphosphine for 16h to furnish the macrolide 10 in 52% yield as a 1.5:l mixture of
isomers. The 15.5-15.7 Hz coupling constants for the
10 O
olefinic hydrogens suggested that the product was a mixture
of diastereomeric acetates, both with ( E ) geometry, rather
than ( E ) and (2)olefins. This conclusion was confirmed by
the catalytic hydrogenation of the product mixture to a similar mixture of saturated isomeric macrolides 11. The
chemoselectivity of the cyclization is established by the reaction of diyne 14 [Eq. (g)], readily available from our Pd-catalyzed coaddition of the terminal acetylene 12 with ynoate 13
5% TDMPP, 5%[Pd(OAc)~l
0 5 1t BuMe,
(TDMPP = tris(2,6-dimethoxyphenyl)phosphine, DCE =
1,2-dichloroethene, DMAP = 4-dimethylamin0pyridine).[~~
The excellent yield of macrodiolide 15 (87-90 %) illustrates
the innocuousness of the normally reactive yneoate units in
substrate 14 under these reaction conditions. The
diastereoselectivity here (4: 1) is higher than that observed in
the cyclization leading to 10 and suggests that the
diastereoselectivity depends upon substituents on the tether.
To our knowledge the Pd-catalyzed sequence of intramolecular redox reaction and addition described here leading to
synthetically interesting geminal dicarboxylates is unprecedented. It stands in contrast to the Pdo catalyzed substitution
reactions of propargyl carbo~ylates[~]
and the Pd2 catalyzed additions of carboxylic acids to triple bonds."'] The
isomerization of an alkyne to an alkene was reported recently,
however, as the first step in the isomerization of alk-2-ynedi1,4-ols to 1 ,Cdicarbonyl compounds.[2b1Rhodium and ruthenium complexes also have been reported to catalyze direct
addition to triple bonds." The new reaction described here
also exhibits excellent atom economy and should allow access to highly functionalized macrolides.
[I] Cf. Cr: M. Sodeoka, H. Yamada, M. Shibasaki, J. Am. Chem. Sac. 1990,
112,4906;Fe: N. Iranpoor, E. Mottaghinejad, J. Organornet. Chem. 1992,
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1979, f01, 7430; J. U. Strauss, P. W. Ford, Tetrahedron Lett. 1975, 2917;
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85, 1549; M. Brock, A. Heesing, Chem. Ber. 1989, f22,1925; Rh and Ru:
B. M. Trost, R. J. Kulawiec, Tetrahedron Lett. 1991, 32, 3039; S . H.
Bergens, B. Bosnich, J. Am. Chem. Soc. 1991, 113, 958; W. Smadja, G.
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1978,2, 355; D. Ma, X. Lu, Tetrahedron 1990,46, 3189, 6319; Pt: H. C.
Clark, H. Kurosawd, Chem. Commun. 1972, 150.
[2] Pd: a) B. M. Trost, T. Schmidt, J. Am. Chem. Soc. 1988,110,2301; b) X.
Lu, J. Ji, D. Ma, W. Shen, L Org. Chem. 1991,56,5774;c) C. Guo, X. Lu,
Tetrahedron Lett. 1991,32, 7549; d) H. Sheng, S. Lin, Y. Huang, ibid. 1986,
27, 4893.
[3] H. Nemoto, H. N. Jimenez, Y. Yamamoto, J. Chem. Sac. Chem. Commun.
1990, 1304.
[4] 8. M. Trost, Science 1991, 254, 1471.
[5] For some of our recent work see, B. M. Trost, B. A. Vos, C. M. Brzezowski, D. P. Martha, Tetrahedron Lett. 1992,33,717; B. M. Trost, Y. Shi,
J. Am. Chem. Sac. 1992, 114, 791; B. M. Trost, M. K. Trost, Tetrahedron
Lett. 1991, 32, 3647; B. M. Trost, Y Kondo, ibid. 1991, 32, 1613; B. M.
Trost, M. K. Trost, 1 Am. Chem. Soc. 1991,113,1850; B. M. Trost, Y. Shi,
ibid. 1991, 113, 701; B. M. Trost, M. Lautens, C. Chan, D. J. Jebaratnam,
T. Miiller, ibid. 1991, ff3, 636; B. M. Trost, Acc. Chem. Res. 1990, 23, 34;
B. M. Trost, S. Matsubara, J. Caringi, J. Am. Chem. Sac. 1989,f f f, 8745.
161 Cf. R. C. Larock, N. G. Berrios-Pena, C. A. Fried, J Org. Chem. 1991,56,
2615; K. Koerber, J. Gore, J.-M. Vatele, Tetrahedron Lett. 1991, 32, 1187;
J. S. Prasad, L. S. Liebeskind, ibid. 1988, 29, 4253, 4257; M. Ahmar, J. J.
Barrieux, B. Cazes, J. Gore, Tetrahedron 1987, 43, 513; N. Chatani, T.
Takeyasu, T. Hanafusa, Tetrahedron Lett. 1986, 27, 1841.
[7] B. M. Trost, J. Vercauteren, Tetrahedron Lett. 1985, 26, 131.
[8] B. M. Trost, C. Chan, G. Riihter, J. Am. Chem. Soc. 1987, 109, 3486.
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D. Milstein, N. J. Taylor, 1 Am. Chem. Soc. 1987, 109, 6385.
Chemoenzymatic Syntheses of the Optically Active
Hydroperoxides of Phosphatidylglycerol
and Phosphatidylethanolamine
with Lipase, Lipoxygenase, and Phospholipase D **
By Kenji Yoneda, Keiji Sasakura, Shoichi Tahara,
Junkichi Iwasa, Naomichi Baba*, Takao Kaneko,
and Mitsuyoshi Matsuo
Recent studies have demonstrated that in vivo formation
of lipid peroxides is responsible for aging and for some serious diseases and dysfunctions such as arteriosclerosis or cancer . [ l ]
For studies in this field, different types of pure, optically
active lipid hydroperoxides are urgently needed. We previ-
Experimental Procedure
Acetic acid (0.150 mL, 2.62 mmol) was added to a solution of 3 (33.8 mg,
0.0327 mmol) and triphenylphosphine (89.1 mg, 0.340 mmol) in toluene
(20 mL) at 20-30°C. After 5min 4 a (325 mg, 1.54 mmol) was added and the
resultant mixture heated at reflux for 20h. The reaction mixture was concentrated under vacuum and the residue chromatographed directly (silica gel,
hexane/ethyl acetate, 10: 1) to give 5 a (379.5 mg, 91 % yield).
Received: May 2, 1991 [Z5328IE]
German version: Angew. Chem. 1992, 104, 1392
0 VCH Verlagsgesellschaft mbH, W-6940 Weinheim, 1992
[*I Prof. Dr. N. Baba, K. Yoneda, K. Sasakura, S. Tahara, Prof. Dr. J. Iwasa
Bioresources Chemistry, Faculty of Agriculture
Okayama University
1-1-1 Tsushimanaka, Okayama 700 (Japan)
Dr. T. Kaneko, Dr. M. Matsuo
Tokyo Metropolitan Institute of Gerontology
35-2 Sakaecho, Itabashiku, Tokyo 173 (Japan)
[**I This work was supported by the Ministry of Education of Japan (grant
0455 6015).
0570-0833/Y2/1010-1336S 3.50t .25/0
Angew. Chem. Int. Ed. Engl. 1992, 31, No. 10
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intermolecular, intramolecular, reaction, cycloisomerization, sequence, redox, additional, catalyzed
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