General method for the palladium-catalyzed allylation of aliphatic alcohols

Article abstract of DOI:10.1021/jo0301907

A palladium catalysis-mediated approach to coupling aliphatic alcohols with allyl carbonates has been developed. The method allows for the allylation of primary, secondary, and tertiary alcohols efficiently under mild conditions. Limitations were explored as well as the asymmetric application of the chemistry. Regiochemical and olefin geometry was controlled in the coupling of unsymmetrical allylating agents. Transient allyl carbonates were observed in the coupling, which comprised the trans-carboxylation of the allyl-carbonate with the requisite alcohol.

Full text of DOI:10.1021/jo0301907

Gen er a l Meth od for th e P a lla d iu m -Ca ta lyzed Allyla tion of
Alip h a tic Alcoh ols
Anthony R. Haight,* Eric J . Stoner, Matthew J . Peterson,† and Vandana K. Grover‡
GPRD Process Research and Development, Abbott Laboratories, Bldg. R8/ 1, 1401 Sheridan Rd.,
North Chicago, Illinois 60064-6285
anthony.haight@abbott.com
Received J une 6, 2003
A palladium catalysis-mediated approach to coupling aliphatic alcohols with allyl carbonates has
been developed. The method allows for the allylation of primary, secondary, and tertiary alcohols
efficiently under mild conditions. Limitations were explored as well as the asymmetric application
of the chemistry. Regiochemical and olefin geometry was controlled in the coupling of unsymmetrical
allylating agents. Transient allyl carbonates were observed in the coupling, which comprised the
trans-carboxylation of the allyl-carbonate with the requisite alcohol.
In tr od u ction
palladium-catalyzed allylation of alcohols has been uti-
lized to a lesser extent due to the poor nucleophilicity of
alcohols. Most examples of oxygen nucleophiles have been
limited to phenols,8 intramolecular allylations,9 substrate-
specific systems,10 or zinc11 or stannyl12 alkoxides. We
report here on a general13 method for the efficient
allylation of aliphatic primary, secondary, and tertiary
hydroxyl groups under palladium catalysis that does not
require the preparation of metal alkoxides11,12 or the
removal of inorganic salts from the reaction mixtures.
In the course of our work, we required a method for
the preparation of a substituted allyl ether appendage
on a sterically hindered alcohol under mild conditions.14
Typically, allyl ethers are prepared under strongly basic
conditions by alkylation of the metal alkoxide with allyl
halides or pseudohalides in a polar solvent15 or by
The transition metal-catalyzed allylation of nucleo-
philes is a versatile methodology in organic synthesis.1
A variety of nucleophiles such as carbanions,1,2 amines,1,3
sulfides,1,4 and sulfinates,1,5 have been shown to couple
efficiently with palladium π-allyl complexes. With ad-
vances in regioselective6 and enantioselective7 reactions,
the utility of this chemistry continues to expand. The
† Current address: Theravance, Inc., 901 Gateway Blvd., South
San Francisco, CA 94080.
‡ Current address: Department of Microbiology and Immunology,
Vanderbilt University School of Medicine, Nashville, TN 37232-0146.
(1) (a) Comprehensive Asymmetric Catalysis; J acobsen, E. N., Pfaltz,
A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol 2. (b) Trost, B.
M.; Van Vranken, D. L. Chem Rev. 1996, 96, 395. (c) Shibasaki, M. In
Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; J AI
Press: Greenwich, CT, 1996; Vol. 5. (d) Tsuji, J . Palladium Reagents
and Catalysts: Innovations in Organic Synthesis; J ohn Wiley and
Sons: New York, 1995. (e) Harrington, P. J . In Comprehensive
Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson,
G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, pp 798-903.
(2) Some recent examples of allylic alkylations: (a) Pedersen, T. M.;
Hansen, E. L.; Kane, J .; Rein, T.; Helquist, P.; Norrby, P.-O.; Tanner,
D. J . Am. Chem. Soc. 2001, 123, 9738. (b) Nakamura, H.; Aoyagi, K.;
Shim, J .-G.; Yamamoto, Y. J . Am. Chem. Soc. 2001, 123, 372. (c) Trost,
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O. A. J . Org. Chem. 1998, 63, 1748.
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Pfaltz, A. J . Heterocycl. Chem. 1999, 36, 1437. (d) Ruwano, R.; Nishio,
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Trost, B. M. Chem. Rev. 1996, 96, 355.
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1995, 14, 4585. (b) Goux, C.; Lhoste, P.; Sinou, D. Synlett. 1992, 725.
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Kloosterman, M.; Van Boom, J . H. Recl. Trav. Chim. Pays-Bas 1983,
102, 501.
(3) Some recent examples of allylic aminations: (a) Konno, T.;
Nagata, K.; Ishihara, T.; Yamanaka, H. J . Org. Chem. 2002, 67, 1768.
(b) You, S. L.; Zhu, X. Z.; Luo, Y. M.; Hou, X. L.; Dai, L. X. J . Am.
Chem. Soc. 2001, 123, 7471. (c) Tietze, L. F.; Schirok, H.; Wohrmann,
M.; Schrader, K. J . Org. Chem. 2000, 65, 2433. (d) Sirisoma, N. S.;
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Mori, M.; Suzuki, A.; Miyaura, N. J . Organomet. Chem. 1996, 525,
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(d) Moreno-Manas, M.; Pleixats, R.; Villarroya, M. Tetrahedron 1993,
49, 1465.
(5) Some recent examples of sulfinates: (a) Danjo, H.; Tanaka, D.;
Hayashi, T.; Uozumi, Y. Tetrahedron 1999, 55, 14341. (b) Hiroi, K.;
Makino, K. Chem. Pharm. Bull. 1988, 36, 1744. (c) Hiroi, K., Makino,
K. Chem. Lett. 1986, 617.
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(13) An application of this chemistry has already been published
on the basis of personal communications: Marmsa¨ter, F. P.; Vanecko,
J . A.; West, F. G. Tetrahedron 2002, 58, 2027.
10.1021/jo0301907 CCC: $25.00 © 2003 American Chemical Society
Published on Web 09/24/2003
8092
J . Org. Chem. 2003, 68, 8092-8096

Palladium-Catalyzed Allylation of Aliphatic Alcohols
TABLE 1. Allyla tion s of Alcoh olsa
a
b
Reactions in THF at 60-65 °C for 1-3 h with 1-3 mol % Pd(OAc)2/2-6 mol % Ph3P. HPLC yield. c Reaction run with 1-3 mol %
(Ph3)4Pd. Reaction run with 2-4 mol % Pd2(dba)3/4-8 mol % Ph3P. e 7a , primary ether; 7b, secondary ether; 7c, bis-ether. f GC yield.
d
alkylation of stoichiometric alkoxyorganostannane de-
rivatives.16 Notably absent from this methodology have
been efforts to allylate sterically hindered aliphatic
alcohols.17
Rhodium-18 and palladium-catalyzed19 allylations have
recently been explored in an effort to allylate hydroxyl
functionalities. In Sinou’s report on the palladium-
catalyzed allylation of carbohydrate substrates using allyl
ethyl carbonate, 2a ,19 an excess of 2a was required
presumably due to the spectator ethoxide competing for
the π-allyl palladium species.19c We reasoned that the
sterics of the spectator alkoxide could be modulated to
competitively favor allylation of the desired alcohol.
catalytic tetrakis(triphenylphosphine)palladium(0)21 to
obtain ether 3a (eq 1; Table 1, entries 1-3). A sufficient
amount of the allyl carbonates was added to convert
>98% of the substrate alcohol, 1a , to the allyl ether, 3a .
This called for 3.3, 2.0, and 1.2 equiv of 2b, 2c, and 2d ,
respectively, for the allylation of 1a (Table 1, entries
1-3). In the allylation of the secondary alcohol, 1b, >5
equiv of either 2b or 2c was necessary to push the
allylation to >95% conversion, compared to 1.5 equiv of
2d (Table 1, entries 4-6).
High yields and minimal amounts of tert-butyl allyl
ether were observed in the allylation of primary and
secondary alcohols when carbonate 2d was employed
(Table 1, entries 3, 6). Unfortunately, no significant
regioselectivity was seen in the allylation of diol 6, which
yielded ethers 7a , 7b, and 7c in a 1:2:1 ratio using 1.1
equiv of 2d (Table 1, entry 8).22 Coupling to tertiary
alcohols is possible with 2d ; however, 5 equiv of 2d is
necessary to obtain high conversion due to competitive
allylation (Table 1, entry 7).
To test this hypothesis, we studied the allylation of
3-phenylpropan-1-ol, 1a , with three allyl carbonates:
allyl methyl carbonate, 2b, allyl isopropyl carbonate, 2c,
and allyl tert-butyl carbonate, 2d .20 The carbonates were
added to a refluxing THF mixture of alcohol 1a and
(14) (a) Stoner, E. J .; Peterson, M. J .; Ku, Y. Y.; Cink, R. D.; Cooper,
A. J .; Deshpande, M. N.; Grieme, T.; Haight, A. R.; Hill, D. R.; Hsu,
M. C.; King, S. A.; Leanna, M. R.; Lee, E. C.; McLaughlin, M. A.;
Morton, H. E.; Napier, J . J .; Plata, D. J .; Raje, P. S.; Rasmussen, M.;
Riley, D.; Tien, J . J .; Wittenberger, S. J . U.S. Patent 6437106 B1,
August 20, 2002. (b) Stoner, E. J .; Allen, M. S.; DeMattei, J . A.; Haight,
A. R.; Leanna, M. R.; Patel, S. R.; Plata, D. J .; Premchandran, R. H.;
Rasmussen, M. J . Org. Chem. 2003, in press.
(15) Guibe, F. Tetrahedron 1997, 53, 13509 and references therein.
(16) (a) Nashed, M. A. Carbohydr. Res. 1978, 60, 200. (b) Alais, J .;
Maranduba, A.; Veyrieres, A. Tetrahedron Lett. 1983, 24, 2383. (c) Gigg,
J .; Gigg, R.; Payne, S.; Conant, R. J . Chem. Soc., Perkin Trans. 1 1987,
1757.
(17) Wess, G.; Kramer, W.; Bartmenn, W.; Enhsen, A.; Glombik, H.;
Muller, H.; Bock, K.; Dries, A.; Kleine, H.; Schmitt, W. Tetrahderon
Lett. 1992, 33, 195.
(18) Evans, P. A.; Leahy, D. K. J . Am. Chem. Soc. 2000, 122, 5012.
(19) (a) Lakhmiri, R.; Lhoste, P.; Kryczka, B.; Sinou, D. J . Carbo-
hydr. Chem. 1993, 12, 223. (b) Lakhmiri, R.; Lhoste, P.; Sinou, D.
Synth. Commun. 1990, 20, 1551. (c) Lakhmiri, R.; Lhoste, P.; Sinou,
D. Tetrahedron Lett. 1989, 30, 4669.
We found that the acidity of the substrate alcohol
influences the selectivity of the reaction.23 In the coupling
of the highly acidic tertiary alcohol 8, only 1.2 equiv of
the carbonate 2d was required to obtain >98% conversion
to the allyl ether, 9, as compared with 5.0 equiv in the
allylation of 4 (Table 1, entries 7 vs 9).24 In a competition
(20) 2b was purchased from Aldrich Chemical Co. 2c was prepared
from allyl alcohol and isopropyl chloroformate. 2d was prepared from
(BOC)2O. See: Houlihan, F.; Bouchard, F.; Fre`chet, J . M. J .; Willson,
C. G. Can. J . Chem. 1985, 63, 153.
(21) Preparing the presumed active catalytic species either from
(Ph3P)4Pd or in situ from Pd(OAc)2/Ph3P or Pd2(dba)3/Ph3P showed no
difference in reactivity or selectivity.
(22) Masaki, Y.; Miura, T.; Ochiai, M. Synlett 1993, 847.
(23) Regioselectivity has been correlated to hydroxyl acidity. See ref
19a: and Massacret, M.; Lhoste, P.; Lakhmiri, R.; Parella, T.; Sinou,
D. Eur. J . Org. Chem. 1999, 2665.
J . Org. Chem, Vol. 68, No. 21, 2003 8093

Haight et al.
SCHEME 1. P r op osed Allyla tion Mech a n ism
experiment comparing the acidity effect to the sterics of
the nucleophile, allylation of an equimolar mixture of
primary alcohol 1a and tertiary alcohol 8 with 1.0 equiv
of 2d gave 8:1 (9:3a ) selectivity favoring tertiary ether
9. This is in stark contrast to allylation under anionic
conditions with KOtBu and allyl iodide, which favors 3a
in a 2:1 ratio (eq 2).
SCHEME 2. Ca r bon a te Isom er iza tion
High regio- and chemoselectivity was observed in the
coupling of 1.2 equiv of tert-butyl cinnamyl carbonate 10
with either 1a or ethanol (Table 1, entries 10, 11). When
ethanol was coupled with the secondary carbonate 13,
only the terminal (E)-alkene 1225 was observed, as
expected from a π-allyl palladium intermediate (Table
1, entry 12). Alkyl substituents on the allyl portion of
the carbonate fail to give acceptable yields in the coupling
with benzyl alcohol even if a huge excess of the alcohol
is employed (Table 1, entries 13, 14).26
Under comparable conditions and time, Pd(PPh3)4 gave
higher conversions in the coupling of 2d with 1a relative
to the catalyst prepared from Pd(OAc)2 and Ph3P (>95
vs 88%, respectively). Triphenylphosphine, dppf, dppb,
and (p-CF3C6H4)3P all were acceptable ligands for the
coupling of 2d with 1b, while Cy3P, (o-tol)3P, or Ph3As
gave either poor conversions or a significant amount of
side-products. In terms of solvents, THF, DME, and
toluene all gave comparable yields in the reaction, while
acetonitrile and DMF generated significant side-products.
19. Addition of the alkoxide to the π-allyl palladium
species then is proposed to yield the product, 20, regen-
erating the Pd(0) catalyst.
A typical procedure was to add Pd(OAc)2 (0.005 equiv)
and Ph3P (0.04 equiv) to a 0.5 mM anhydrous degassed
THF solution of 1b with 2d (1.5 equiv). The mixture was
heated to reflux for 3 h, concentrated, and purified by
column chromatography to yield 3b in 92% yield.
To our surprise, when we monitored by HPLC the
coupling of ethanol with carbonate 10 at 35 °C, we
observed the transient appearance of the ethyl carbonate,
21 (Scheme 2).29 As the reaction progressed, the ratio of
21 to 10 present in the mixture shifted from 90:10 (21:
10) at 4% conversion to 45:55 (21:10) at 89% conversion.
The equilibrium ratio of 21 to 10 is approximately 10:1
as established by monitoring a 35 °C THF solution of an
equimolar mixture of 10 and ethanol in the presence of
Pd2(dba)3/(o-furyl)3P under which conditions little cou-
pling is observed. As expected, control experiments
demonstrated that both palladium and a phosphine
ligand are necessary for the formation of carbonate 21.
π-Allyl palladium(II) alkyl carbonate complexes are
known to react rapidly with water to generate hydrogen
carbonate complexes.30 We are aware of only one example
where such a transalkoxylation has been demonstrated
with an alcohol.31 The observation of the ethyl carbonate
21 during the coupling of 10 with ethanol would suggest
that these transalkoxylation reactions are more general
In situ analysis shows the mechanism to be more
complex than the literature would suggest for π-allyl
palladium chemistry.1,27 The generally accepted mecha-
nism for allylations with allyl carbonates invokes the
reversible28 oxidative addition of 2d to Pd(0) to give
π-allyl palladium intermediate 17 (Scheme 1).1,27 Decar-
boxylation yields the alkoxide intermediate 18, which is
in rapid protic equilibrium with the substrate alkoxide
(24) Low isolated yield of 9 appears to be due to the stability of the
material during isolation.
(25) Barluenga, J .; Alonso-Cires, L.; Campos, P. J .; Asensio, G.
Tetrahedron 1984, 40, 2563.
(26) Recently reported solution to this problem employs a zinc
alkoxide as the nucleophile.11
(27) (a) Amatore, C.; J utand, A. J . Organomet. Chem. 1999, 576,
254. (b) Backvall, J . E.; Nordberg, R. E.; Vaagberg, J . Tetrahedron Lett.
1983, 24, 411. (c) Suzuki, T.; Fujimoto, H. Inorg. Chem. 1999, 38, 370
and references therein.
(28) (a) Amatore, C.; Gamez, S.; J utand, A.; Meyer, G.; Moreno-
Manas, M.; Morral, L.; Pleixats, R. Chem. Eur. J . 2000, 6, 3372. (b)
Amatore, C.; J utand, A.; Meyer, G.; Carelli, I.; Chiarotto, I. Eur. J .
Inorg. Chem. 2000, 1855. (c) Amatore, C.; J utand, A.; Mayer, G. Chem.
Eur. J . 1999, 5, 466.
(29) Carbonate 21 was independently prepared from cinnamyl
alcohol and ethylpyrocarbonate for comparison (Cravotto, G.; Gioven-
zana, G. B.; Sisti, M.; Palmisano, G. Tetrahedron 1998, 54, 1639).
(30) Ozawa, F.; Son, T.; Ebina, S.; Osakanda, K.; Yamamoto, A.
Organometallics 1992, 11, 171.
8094 J . Org. Chem., Vol. 68, No. 21, 2003

Palladium-Catalyzed Allylation of Aliphatic Alcohols
TABLE 2. Asym m etr ic Allyla tion of (-23 w ith Ben zyl
and might offer a method of preparing mixed carbon-
ates.33
Alcoh ola
In the coupling of carbonate 13, rapid formation of the
(E)-cinnamyl carbonate 10 was initially observed, fol-
lowed by carbonate 21 and ultimately allyl ether 12
(Scheme 2). The isomerization of the secondary carbonate
13 to the more stable 10 is the result of the reversibility
of the oxidative addition/reductive elimination process.34
We investigated the effect of the nucleophile structure
on the rate of the alcohol allylation reaction. Under the
standard conditions of Pd2(dba)3 (5 mol % Pd) and Ph3P
(10 mol %) in THF (0.25 M) at 55 °C, coupling of
carbonate 10 with tert-butyl alcohol, ethanol, and 2,2,2-
trifluoroethanol gave relative rates of 1, 18, and 833,
respectively. The rate differences between ethanol and
tert-butyl alcohol can be attributed to a steric differentia-
tion between the two. The surprisingly fast reaction with
2,2,2-trifluoroethanol, an alcohol of extremely low nu-
cleophilicity, suggests to us that the reaction rate is
highly sensitive to either formation or concentration of
the alkoxide.
Organotin alkoxides have previously been shown to be
efficient coupling partners with π-allyl palladium spe-
cies,12 presumably due to their enhanced nucleophilicity.
Unfortunately, preparation of the stannyl ethers and
removal of the stannyl byproducts is a hindrance to this
approach. We found that when the coupling of ethanol
with 10 was carried out under the standard conditions,
addition of 10 mol % tributyltin ethoxide generated 12
much more rapidly, avoiding the need for preparation the
stannyl ethers and reducing the concerns for removal of
stoichiometric amounts of organotin byproducts (eq 3).
config-
uration
entry
ligand
(R,R)-BDPP
(R,R)-BDPP
24
time (h)
eeb
30%
28%
25%
nd
65-88%
73%
9%
9%
5%
41%
6%
41%
16%
1
2
30%
>98%
>98%
2%
>98%
>98%
>98%
>98%
50%
>98%
10%
>98%
>98%
3
8
4
24
8
8
<1
<1
4
4
24
1
R
R
R
nd
R
S
R
S
S
R
R
R
S
3c (R,R)-BDPP
4
5
6
7
8
(R,R)-DiACyh-PyCard
(R)-BINAP
(S)-BINAP
(S,S)-DIOP
(R,R)-DIOP
(R,R)-EtDuphos
(R,R)-Norphos
(R)-Quinap
(R,R)-Me-BPE
(R)-MOP
9
10
11
12
13
20
a
Reaction in 0.1 M THF at reflux with 14 (6 equiv), 1 mol %
b
Pd2(dba)3, and 4 mol % ligand. Chiral HPLC for yield and
d
enantiomeric purity. c Performed with 10% Bu3SnOEt. C(-)-
N,N′-(1R,2R)-1,2-Diaminocycohexanediylbis-(2-pyridinecarboxam-
ide).
conditions, this suggests to us that a competitive catalyst
may be involved.
The absolute stereochemistry of 24 was determined
from a sample of synthesized using (R)-BINAP as the
ligand. The alkene was first reduced followed by selective
36
benzylic oxidation with RuCl3/NaIO4 to give, after
hydrolysis, the known secondary alcohol 25 (eq 5).37 The
sense of stereochemical induction is consistent with that
observed in the malonate alkylation of the comparable
π-allyl palladium complex prepared from the acetate,38
as well as the stereochemistry obtained in the coupling
with phenol.39
To further expand the utility of this chemistry, we
explored the enantioselective alkylation of secondary
carbonate 23 with various ligands (Table 2).35 Only in
the case of BINAP was good conversion (>99%) and
moderate enantiomeric excess (73-88%) observed in the
coupling (entries 5, 6). Careful monitoring of the coupling
with BINAP revealed that the enantiopurity of the
product, 24, decreased as the reaction progressed. Since
the product was shown to be stable under the reaction
In conclusion, this work demonstrates that employing
the sterically hindered spectator tert-butyl alkoxide in
(35) (a) BDPP: Xiao, W.-J .; Alper, H. J . Org. Chem. 2001, 66, 6229.
(b) (-)-N,N′-(1R,2R)-1,2-Diaminocyclohexanediylbis(2-pyridinecarbox-
amide): Trost, B. M.; Hachiya, I. U.S. Patent 6,130,349, 1998. (c)
DIOP: Iourtchenko, A.; Sinou, D. J . Mol. Catal. A: Chem. 1997, 122,
91. (d) EtDuphos: Burk, M. J . J . Am. Chem. Soc. 1991, 113, 8518. (e)
Norphos: Brunner, H.; Deml, I.; Dirnberger, W.; Ittner, K.; Reisser,
W.; Zimmermann, M. Eur. J . Inorg. Chem. 1999, 1, 51. (f) Quinap:
Rabeyrin, C.; Nguefack, C.; Sinou, D. Tetrahedron Lett. 2000, 41, 7461.
(g) Me-BPE: Burk, M. J . J . Am. Chem. Soc. 1991, 113, 8518. (h)
MOP: Kodama, H.; Taiji, T.; Ohta, T.; Furukawa, I. Tetrahedron:
Asymmetry 2000, 11, 4009.
(36) Booker-Milburn, K. I. Tetrahedron 1997, 53, 12319.
(37) Node, M.; Nishide, K.; Shigeta, Y.; Shiraki, H.; Obata, K. J .
Am. Chem. Soc. 2000, 122, 1927.
(38) Trost, B. M.; Murphy, D. J . Organometallics 1985, 4, 1143.
(39) BINAP with phenol: Iourtchenko, A.; Sinou, D. J . Mol. Catal.
A: Chem. 1997, 122, 91.
(31) Davis, A. P.; Dorgan, B. J .; Mageean, E. R. J . Chem. Soc., Chem.
Commun. 1993, 492. Alkyl allyl carbonates have been prepared via
palladium catalysis.32
(32) McGhee, W. D.; Riley, D. P.; Christ, M. E.; Christ, K. M.
Organometallics 1993, 12, 1429.
(33) Carbonate 21 decomposes to ether 12 in THF at 34 °C in the
presence of Pd2(dba)3/Ph3P. No transient intermediates could be
detected by HPLC in this reaction. However, carbonate 10 was
observed in situ to be present prior to and during the formation of
ether 12 in the decomposition of carbonate 21 under the same
conditions with 1 equiv of tert-butyl alcohol present. A trace of the
tert-butyl ether was also observed by LC/MS in the crude reaction
product, but it could not be isolated.
(34) Catalyzed sigmatropic rearrangement cannot be ruled out at
this time.
J . Org. Chem, Vol. 68, No. 21, 2003 8095

Haight et al.
the allyl carbonate moiety gives a general method for the
allylation of aliphatic primary, secondary, and tertiary
alcohols under conditions amenable to complex sub-
strates.13,14 The mechanism for the coupling is complex
due, in part, to a number of equilibria that exist with
regards to the allyl carbonate species as well as the
nucleophile employed. Further studies of the catalyst
system are being pursued to improve the understanding
as well as the utility of the chemistry.
Ack n ow led gm en t . The authors thank David
Barnes, Steven King, and Steven Wittenberger for
helpful discussions.
Su p p or tin g In for m a tion Ava ila ble: Experimental pro-
cedures and spectral data for starting materials 8, 15, 13, and
23 and products 3a , 3b, 5, 11, 12, 16, and 24 and selected
elemental analyses thereof. This material is available free of
charge via the Internet at http://pubs.acs.org.
J O0301907
8096 J . Org. Chem., Vol. 68, No. 21, 2003