SODIUM 1
Naphthalenide radical anion forms.7 Though the reduction po-
Sodium1
tential of this system is similar to that of sodium in other solvents
(a half-wave potential of -2.5 V8 vs. -2.96 V in HMPA6b and
Na
-2.59 Vin NH31b), side reactions are often minimized, and re-
ductions are sometimes titrated to color end-point. Other additives
[7440-23-5] Na (MW 22.99)
such as anthracene and benzophenone result in solutions with de-
InChI = 1/Na
creased, more selective, reducing power, though this has been
InChIKey = KEAYESYHFKHZAL-UHFFFAOYAO
rarely exploited.8
(powerful one-electron reducing agent for most functional
Reduction of Unsaturated Bonds. The classical reduction
groups;1 reductively couples ketones and esters to unsaturated
of ketones with sodium in alcohol, along with the mechanistically
carbon atoms;2 reductively eliminates and couples halogens and
similar reduction in ammonia with added proton donors, still finds
other groups; can be used to generate alkoxides)
use in certain systems where the desired stereochemistry cannot
ć%
Physical Data: mp 97.8 C; d 0.968 g cm-3.
be generated by metal hydrides (see also Lithium).1d-g The am-
Solubility: sol liquid NH3; slightly sol ethereal solvents; dec in
monia system is preferred, minimizing epimerization of ketones
alcohols; reacts violently in H2O.
and equilibration of product alcohols. NH4Cl has been recom-
Form Supplied in: silver-white or gray solid in brick, stick, or
mended as proton donor to suppress hydrogen transfer,9 though
ingot form; more commonly as 3 8 mm spheres or as a disper-
this requires a large excess of sodium;10 using several equivalents
sion in various inert oils.
of a primary alcohol also minimizes this side reaction.11 Alco-
Purification: surface oxide can be removed by heating in
hols, ethers, amines, carboxylic acids, and isolated internal double
toluene;3 oxide impurities can usually be ignored.
bonds are unaffected, but most other functional groups have re-
Handling, Storage, and Precautions: the dry solid quickly oxi-
duction potentials less negative than aliphatic ketones. Aromatic
dizes when exposed to air and in very moist air is potentially
ketones and Ä…-heteroatom-substituted ketones are generally un-
flammable. The highly corrosive sodium vapor ignites sponta-
suitable substrates for these reductions.
neously in air, and is a severe irritant to eyes, skin, and mu-
Reductions are kinetically controlled, though the literature con-
cous membranes. Utmost care should be taken to keep sodium
tains several mistaken assumptions on this point; stereochemistry
away from halogenated solvents, oxidants, and aqueous min- is determined by pyramidalization of the ketyl and subsequent
eral acids. Fires should be quenched with a dry powder such
carbanion intermediates, and prediction of the stereochemical re-
as Na2CO3, NaCl, or NaF; water, CO2, Halon, and silica gel
sult is in most cases extremely difficult. Study of certain systems
should be avoided. Excess sodium is best disposed of by slow
does allow a few general remarks to be made. Unhindered cyclo-
introduction into a flask of isopropanol, possibly containing 1%
hexanones usually give larger equatorial:axial ratios than can be
water, taking care to vent liberated H2, and neutralizing the re-
obtained with metal hydrides or by equilibration.12 Generation of
sulting solution with aqueous acid. Sodium stored under oil is
equatorial alcohols from hindered cyclohexanones often requires
best weighed by rinsing freshly cut pieces with hexane and after
the use of dissolving metals, while metal hydrides can give exclu-
evaporation adding to a tared beaker containing hexane.
sively the axial product (eqs 1 and 2).13 Bicyclo[2.2.1]heptan-2-
ones always provide an excess of the endo-alcohol (eq 3).14,15
O
Original Commentary Na
NH3, EtOH
100%
Michael D. Wendt
Abbott Laboratories, Abbott Park, IL, USA
HO HO
Reaction Conditions. Sodium, along with the other com-
+ (1)
monly used alkali metals Lithium and Potassium, is an extremely
powerful one-electron reductant. Historically, solutions of sodium
in ammonia have been used to reduce a wide variety of functional
94:6
groups (see also Sodium Ammonia for some of these transforma-
tions, particularly the Birch reduction of aromatic rings).4 These
reductions are usually carried out in the presence of proton donors,
O O
Na
normally simple alcohols or NH4Cl, though occasionally these
O EtOH, " O
O
(2)
are added prior to workup. Many reductions are performed with
95%
OH
solutions of sodium in refluxing alcohols; here a large excess of
sodium is often required due to its gradual decomposition to alkox-
ides and H2. It is sometimes simpler to add a mixture of alcohol
and substrate to a dispersion of sodium in an inert solvent such as
Na
toluene. HMPA is also occasionally employed as a solvent;5 solu-
i-PrOH, "
(3)
tions of sodium in HMPA behave similarly to those in ammonia.6
58%
While sodium is insoluble in solvents such as DME or THF, naph-
O
HO
thalene is usually included, and a green solution of the Sodium
Avoid Skin Contact with All Reagents
2 SODIUM
Imines are reduced to amines in good yield by sodium in tem (eqs 8 and 9).31 Conjugated dienes are reduced via a cis-
alcohols, probably through a similar mechanism. In the absence of radical anion,32 while, with lithium, trans-dianions may play
proton donors, reductive dimerization dominates.16 1,3-Diimines, a role. Dimerization and regioisomer formation usually pre-
which exist as tautomeric enamino imine mixtures, are reduced clude the use of sodium, though exceptions exist.33 A few
to diastereomeric mixtures of diamines (eq 4).17 Allylic imines reports of homoconjugated diene reduction have appeared.34
have been reduced to alkenes.18 Reduction of oximes by sodium
in alcohol is particularly useful,19 since Lithium Aluminum Hy-
HH
dride can produce Beckmann rearrangements or aziridines.20,21 Na
+ (8)
Bicyclo[2.2.1]heptan-2-one and tricyclo[2.2.1.02,6]heptan-3-one
t-BuOH
HMPA
oxime reductions yield predominantly endo-amines (eq 5).21,22
H H
91:3
Ph Ph
Na
N N NH NH2
i-PrOH
(4)
Ph Ph 98% Ph Ph
HH
Na
+ (9)
t-BuOH
Na
HMPA
H H
EtOH, "
NH2 +
(5)
73:27
50%
Et NOH Et Et
NH2
14:86
Pinacol Coupling Reactions. In the absence of proton donors,
The reduction of esters to alcohols with sodium in alcohol reductions of carbonyl compounds often lead to significant
(Bouveault Blanc reduction)23 has been all but supplanted by the amounts of reductively coupled products, but the intentional pina-
use of metal hydrides. Where an ester must be reduced in the pres- col coupling of ketones with sodium in inert solvents is typically
ence of an acid, an improved procedure run in ammonia can be a low-yielding, unselective process. Milder conditions utilize lan-
used effectively (eq 6).24 thanoids and low-valent transition metals, particularly titanium.35
Sodium is used only in cases where no other functional groups
Na
CO2Me
are present.36 Sodium is often employed in related intramolecular
NH3, EtOH
OH
(6)
couplings with unsaturated carbon carbon bonds, forming five-
72%
CO2H CO2H
and six-membered rings regio- and (often) stereoselectively.37
Ketyls cyclize onto allylic systems with anti displacement
Dissolving metal reductions of Ä…,²-unsaturated carbonyl com-
(eqs 10 and 11).38 Transannular cyclizations have also been
pounds are almost always performed with lithium in ammonia
demonstrated.39 Alkynes are cyclized similarly (eq 12),40 usually
(see Lithium),1d though sodium is occasionally used without any
with Sodium Naphthalenide.41 With allenes, the exo closure prod-
particular change in result. Selected examples of enone reduction
uct is obtained (eq 13),42 though prolonged reaction can scramble
with sodium in HMPA have been examined;6b,25 these are most
the position of the resulting double bond.43
notable for the fact that they tend to produce product mixtures
enriched in the less stable epimer, compared to reactions run in
Na
ammonia (eq 7).25a,1e
THF
O
HO
(10)
64%
CHCOMe Na
OMOM
t-Bu t-BuOH
CH2COMe
CH2COMe + (7)
t-Bu t-Bu Na
O HO
THF
in NH3, THF 84:10 (11)
70%
24:60 OMOM OMOM
in HMPA, THF
The reduction of internal acyclic alkynes to trans-alkenes
by sodium in ammonia is well known.1b Complications in re-
Na
O O O O
ducing terminal alkynes result from deprotonation by NaNH2,
NH3, (NH4)2SO4
(12)
formed in situ. This can be exploited by addition of an equiv-
~90%
alent of NaNH2,26 or overcome by addition of ammonium
O
OH
salts.27 Medium-ring cyclic alkynes often give mixtures of
cis- and trans-alkenes, resulting from partial isomerization by
NaNH2 to allenes,28 which in turn give cis/trans mixtures de-
HO
Na, C10H8
pendent on product stability and the presence or absence of
O "
THF
proton donors.29 Sodium in HMPA/t-BuOH has been shown to
(13)
30%
reduce alkynes;30 internal monoalkenes, inert under most con-
H
ditions, give near-equilibrium mixtures of alkanes with this sys-
A list of General Abbreviations appears on the front Endpapers
SODIUM 3
Na
O O
Acyloin Couplings. Reductions of esters under aprotic con-
t-BuOH, THF
ditions, usually refluxing toluene or xylene, result in Ä…-hydroxy
(18)
Cl O O
75%
ketones, also called acyloins.2 Sodium Potassium Alloy alloy
is also used and allows reaction at lower temperatures. Rigor-
ous exclusion of oxygen during reaction and workup is essential.
Base-catalyzed side reactions are suppressed by the coaddition
Cl
of substrate and Chlorotrimethylsilane, so as to trap the enedi-
Cl Na
Cl
olate and alkoxide products, though good yields can sometimes
EtOH, "
(19)
Cl
be obtained regardless.2,44 Workup is greatly simplified, and the
69%
Cl
acyloins can be freed by treatment with aqueous acid or deoxy-
Cl
genated methanol. Couplings can be performed on esters with
leaving groups at the ²-position (eq 14),45 resulting in a useful
Alcohols are usually derivatized and reduced with metal
cyclopropanone hemiacetal synthesis (eq 15).46
hydrides, though other methods have received attention.57 Among
dissolving metal techniques, lithium or potassium in amines are
TMSO OTMS
most often used to hydrogenolyze various esters. Sodium in
Na, TMSCl
CO2Et
HMPA gives nearly quantitative yields of alkanes from tertiary
(14)
EtS
69%
esters.58 Sodium in ammonia can cleave alkyl mesylates (eq 20),59
EtS
SEt
while phosphate esters or mesylates of phenols are similarly re-
duced to aromatic hydrocarbons.60 Like metal hydrides, sodium in
Na, TMSCl ammonia cleaves epoxides to give the more substituted alcohols,
PhMe, "
OTMS
with the exception of aryl-substituted epoxides (eq 21).61 Lithium
CO2Et
(15)
Cl
61%
OEt and second-row metals, particularly calcium, are also effective for
epoxide cleavages.
Intramolecular acyloin couplings are an enormously success-
ful method for forming four-membered rings.47 Highly strained
Na
NH3, THF
products can undergo subsequent thermal ring opening (eq 16);
O O
O O (20)
O O
Na/K is sometimes more effective in these cases. Hindered diesters 80%
MsO
HN HN
can undergo Ä…,Ä…-bond cleavage prior to reduction.2 Five- and six-
OMe OMe
MeO2C MeO2C
membered rings are routinely generated, often without employing
TMSCl. Larger rings, more difficult to form by other methods, are
Na
also closed in good yields,48 including several polycyclic frame- O
NH3
Ph
Ph
OH (21)
works (eq 17).49 Rings containing 12, 24, and 42 carbon atoms,50
89%
Ph
Ph
paracyclophanes, and rings containing N, O, S, and Si atoms have
been formed.51
Most other aliphatic ethers are inert to dissolving metals, but
benzyl ethers (as well as esters, amines, and thioethers) are readily
OTMS
Na, TMSCl
CO2Me " debenzylated by sodium in ammonia. This is a common deprotec-
CO2Me tion method in peptide and carbohydrate chemistry.62 Substituted
PhMe, " 86%
OTMS
H
H trityl ethers have been used to protect hydroxyl groups in nu-
cleotides. The differing reduction potentials for the p-methoxy-
trityl63 and Ä…-naphthyldiphenylmethyl64 groups allow for selec-
OTMS
tive deprotection using sodium/aromatic hydrocarbon systems
(16)
(eqs 22 and 23). Simple phenyl ethers are cleaved by sodium only
OTMS
with great difficulty.
O
NpPh2CO HO
Na,
FeCl3 Th Th
CO2Me
HCl O O
O
MeO2C
(22)
Na, TMSCl
ether
THF
(17)
87%
PhMe, " 70% p-MeOTrO p-MeOTrO
p-MeOTrO HO
Na,
Th Th
Reduction of Saturated Bonds. Typical Birch reduction con-
O O
(23)
ditions dehalogenate aryl, vinyl, bridgehead, and cyclopropyl
THF, HMPA
92%
halides, though side reactions are often troublesome.52 Alkyl flu-
OH OH
orides are not reduced by sodium under any conditions, requiring
a K/crown ether system.53 Sodium in alcohol/THF is an effec-
While many desulfurizations by alkali metals are known,65 use
tive substitute for Birch conditions;54,55 these conditions can also
of sodium is generally restricted to alkyl aryl thioethers. These
reduce simple alkyl halides (eq 18).36b A simpler procedure em-
are cleaved in the presence of aryl ethers by sodium in HMPA.66
ploying refluxing ethanol is superior in some cases (eq 19).56 Phenyl thioethers are more often cleaved in refluxing alcohols
Avoid Skin Contact with All Reagents
4 SODIUM
O O
(eq 24).67 By substituting TMSCl for the proton source, alkyl or
H
Na
vinyl silanes can be isolated (eq 25).68 Sodium in ammonia has NH3
N N
(30)
been used in a deoxy sugar synthesis where more typical reagents
N N
88%
(Raney Nickel, Nickel Boride, Tri-butylstannane) fail.69
H
O O
OH OH
PhS
Na
Reductive Eliminations. When a leaving group is situated
BuOH, "
(24)
adjacent to a reducible functionality, elimination results. It is gen-
93%
erally agreed that at the site of the initially reduced carbon atom,
an anion is generated which then displaces the leaving group.
Highly strained alkenes have been generated in this way. Usu-
ally vic-dihalides are the immediate precursor (eq 31),81 though
vic-dimesylates have also been used.82 Alkenes have also been
OTMS Na, TMSCl OTMS
C6H6, "
generated from vic-dinitriles83 and more exotic combinations of
SPh TMS
(25)
functional groups.84 Fragmentations of ²-chloro ethers,85 ²,Å‚-
88%
epoxy nitriles,86 and ²-hydroxy nitriles87 have also been demon-
strated, the last undergoing subsequent double bond reduction (eqs
32 34).
Sulfones are hydrogenolyzed by sodium in ethanol.70 This
method is again most often used where commonly preferred
HO HO
methods fail (eq 26),71 and includes a rare application to an Ä…-
Na, C10H8
Cl
DME
substituted carboxylic acid (eq 27).72 Aryl sulfonamides are read-
(31)
73%
ily cleaved to amines with sodium naphthalenide and Sodium
Cl
OMe OMe
Anthracenide.73 Tosylates74,62 and N-tosylsulfoximines75 are
similarly reduced to alcohols and sulfoximines, respectively.
C6H11
Reductive decyanation is effectively performed with sodium
Cl
in ammonia.76 This method complements Sodium Borohydride,
Na
C6H11 THF
which is sometimes ineffective with Ä…-amino nitrile substrates
(32)
O
and provides products with inversion of configuration (eq 28).77 96%
OAc OH
An alternative method employing sodium or preferably potassium
HO
in HMPA/t-BuOH also smoothly removes nitriles.78 Isocyanides
are reduced to hydrocarbons, providing an effective deamination
CN
method (eq 29).79 Rearrangements are largely avoided but, with
Na
O
NH3
acyclic substrates, loss of optical activity results. Finally, one last
HO
(33)
common application of the sodium/ammonia system is the reduc-
90%
tive cleavage of acylated N N bonds (eq 30).80
HO
OMEM
Na
O
Na NC
NH3, EtOH
MeO O
EtOH, THF
SO2Ph
68%
O
80%
MeO MeO
O
MEMO
9
O
OMEM
O
MeO
O
(34)
(26)
MeO
O
MeO
MEMO
10
Na
Wurtz Reaction. The classical intermolecular coupling of
EtOH, THF
CO2H
halides with sodium, mechanistically related to the eliminations
CO2H
(27)
72%
noted above, is of limited use. Cross couplings lead to mixtures of
SO2CH2Ph
desired and homocoupled products, while dimerizations are of lit-
tle synthetic value. Magnesium, lithium, and copper reagents are
Na
Pr
N Pr N
NH3, THF
NC normally employed here.88 Intramolecular couplings frequently
(28)
100% employ sodium, however. Ring closure to form [2.2]phanes is
effective when tetraphenylethylene (TPE) is used catalytically
Na, C10H8 (eq 35).89 Greatest utility is found in the formation of cyclo-
Ph DME Ph
propanes (eq 36),90 and to a lesser extent cyclobutanes (eq 37),91
(29)
NC H
Ph 87% Ph
where Zinc is preferred.
A list of General Abbreviations appears on the front Endpapers
SODIUM 5
has been reported.97 Reactions are run without solvent at room
Na, TPE
temperature, and include bromobenzene as catalyst. This oper-
Br
THF
(35) ationally simple variant of the pinacol coupling favors dl over
44%
Br meso products, particularly for aryl aldehydes and aryl ketones
with electron-withdrawing substituents (eq 40).
O
Na
dioxane
Br Cl (36)
Na, PhBr
78 94%
84%
Br
Na, C10H8
Br
glyme
Br (37)
Br Br
6.5%
OH Br
OH
(40)
Use as a Base. Sodium reacts slowly with alcohols to give
OH
Br OH
solutions of alkoxides. While sodium alkoxides are far more com-
99:1
monly generated by Sodium Hydride, or obtained commercially,
the older method is still occasionally used. The protic Bamford
Stevens reaction uses sodium to generate alkoxides from Ethylene
Reduction of Saturated Bonds. It has been demonstrated
Glycol, present as solvent.92 Sodium methoxide can be substi-
that Birch-type reductions of saccharides, effecting deprotection
tuted, but the original conditions are usually employed. Regiose-
of benzyl ethers and benzenesulfonamides, can be accomplished
lectivity can be a problem; while the more substituted regioisomer
without reaction of anomeric hemiacetal linkages.98 Reactions
usually predominates, prediction is difficult.93 Rearrangements of
were completed in 10 60 min, and examples of multiple deprotec-
cationic intermediates also limit its use, though many successful
tions were reported. 2-Hydroxy sugars were somewhat less stable
examples of this reaction do exist (eq 38).94
to the reaction conditions than 2-amino sugars, but little erosion
HH
Na to alditols was seen even in these cases (eq 41).
ethylene glycol, "
(38)
95%
Related Reagents. Sodium Alcohol; Sodium Alumina;
TsHNN
Sodium Ammonia; Lithium; Potassium.
OBn
BnO
1 Na, NH3, _78 oC
BnO
O
O
O
BnO 2 Ac2O
OH
First Update BnO
76%
OBn
NHSO2Ph
Michael D. Wendt OAc
AcO
Abbott Laboratories, Abbott Park, IL, USA
AcO
O
O (41)
O
AcO
OH
AcO
Reduction of Unsaturated Bonds. Stereochemical control
OAc
NHAc
of dissolving metal cycloalkanone reduction has been shown to
be dependent on counterion association with the ketyl radical an-
ion; exo/endo epimer ratios can be controlled by choosing among
lithium, sodium, or potassium in ammonia, or by addition of ex- 1. (a) House, H. O. Modern Synthetic Reactions; Benjamin: Menlo Park,
CA, 1972. (b) Smith, M. In Reduction: Techniques and Applications in
cess salt.95 Sodium is endo-favoring, though less so than lithium,
Organic Synthesis; Augustine, R. L., Ed.; Dekker: New York, 1968.
while potassium favors exo; thus sodium should not normally
(c) Hudlicky, M. Reductions in Organic Chemistry; Horwood:
be the metal of choice for this reaction. Sodium in refluxing 1-
Chichester, 1984. (d) Caine, D., Org. React. 1976, 23, 1. (e) Pradhan,
propanol has been used to reduce disubstituted 2-amino amides
S. K., Tetrahedron 1986, 42, 6351. (f) Huffman, J. W., Acc. Chem. Res.
to the corresponding alcohols without contamination by diamine
1983, 16, 398. (g) Huffman, J. W., Comprehensive Organic Synthesis
side-products (eq 39).96 Simple amides were also successfully
1991, 8, Chapter 1.4.
transformed to alcohols, but chiral monosubstituted amino amides
2. (a) Finley, K. T., Comn. C.R. Hebd. Seances Acad. Sci. 1964, 64, 573.
were extensively racemized.
(b) Bloomfield, J. J.; Owsley, D. C.; Nelke, J. M., Org. React. 1976, 23,
259.
3. Fieser, M.; Fieser, L. F., Fieser & Fieser 1967, 1, 1022.
4. The Chemistry of Non-Aqueous Solvents; Lagowski, J. J., Ed.; Academic:
NH2 Na, 1-propanol
OH
(39)
New York, 1967; Vol. 2, Chapter 6, 7.
H2N H2N
reflux, 1 h
O
5. Normant, H., Angew. Chem., Int. Ed. Engl. 1967, 6, 1046.
98%
6. (a) Schindewolf, U., Angew. Chem., Int. Ed. Engl. 1968, 7, 190.
(b) Bowers, K. W.; Giese, R. W.; Grimshaw, J.; House, H. O.; Kolodny,
N. H.; Kronberger, K.; Roe, D. K., J. Am. Chem. Soc. 1970, 92, 2783.
Pinacol Coupling Reactions. An improved procedure for
the sodium-mediated reductive coupling of carbonyl compounds 7. Garst, J. F., Acc. Chem. Res. 1971, 4, 400.
Avoid Skin Contact with All Reagents
6 SODIUM
8. Mann, C. K.; Barnes, K. K., Electrochemical Reactions in Non-Aqueous 42. Pattenden, G.; Robertson, G. M., Tetrahedron 1985, 41, 4001.
Systems; Dekker: New York, 1970.
43. Crandall, J. K.; Mualla, M., Tetrahedron Lett. 1986, 2243.
9. Rautenstrauch, V.; Willhalm, B.; Thommen, W.; Burger, U., Helv. Chim.
44. Snell, J. M.; McElvain, S. M., Org. Synth., Coll. Vol. 1943, 2, 114.
Acta 1981, 64, 2109.
45. Rühlmann, K., Synthesis 1971, 236.
10. Grieco, P. A.; Burke, S.; Metz, W.; Nishizawa, M., J. Org. Chem. 1979,
46. Salaün, J.; Marguerite, J., Org. Synth., Coll. Vol. 1990, 7, 131.
44, 152.
47. Bloomfield, J. J.; Nelke, J. M., Org. Synth., Coll. Vol. 1988, 6, 167.
11. Huffman, J. W.; Copley, D. J., J. Org. Chem. 1977, 42, 3811.
48. Bloomfield, J. J.; Owsley, D. C.; Ainsworth, C.; Robertson, R. E., J. Org.
12. (a) Huffman, J. W.; Charles, J. T., J. Am. Chem. Soc. 1968, 90, 6486.
Chem. 1975, 40, 393.
(b) Solodar, J., J. Org. Chem. 1976, 41, 3461.
49. Bartetzko, R.; Gleiter, R.; Muthard, J. L.; Paquette, L. A., J. Am. Chem.
13. (a) Giroud, A. M.; Rassat, A., Bull. Soc. Chem. Fr. 1976, 1881.
Soc. 1978, 100, 5589.
(b) Aranda, G.; Bernassau, J.-M.; Fetizon, M.; Hanna, I., J. Org. Chem.
50. (a) Natrajan, A.; Ferrara, J. D.; Youngs, W. J.; Sukenik, C. N., J. Am.
1985, 50, 1156.
Chem. Soc. 1987, 109, 7477. (b) Ashkenazi, P.; Kettenring, J.; Migdal,
14. Barton, D. H. R.; Werstiuk, W. H., J. Chem. Soc. (C) 1968, 148.
S.; Gutman, A. L.; Ginsburg, D., Helv. Chim. Acta 1985, 68, 2033.
15. (a) Welch, S. C.; Walters, R. L., Synth. Commun. 1973, 3, 419.
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(b) Rautenstrauch, V., J. Chem. Soc., Chem. Commun. 1986, 1558.
Heterocycl. Chem. 1977, 14, 11. (b) Johnson, P. Y.; Kerkman, D. J.,
16. (a) Smith, J. G.; Ho, I., J. Org. Chem. 1972, 37, 653. (b) Jaunin, R.;
J. Org. Chem. 1976, 41, 1768.
Magnenat, J.-P., Helv. Chim. Acta 1959, 42, 328.
52. Vogel, E.; Roth, H. D., Angew. Chem., Int. Ed. Engl. 1964, 3, 228.
17. Barluenga, J.; Olano, B.; Fustero, S., J. Org. Chem. 1983, 48, 2255.
53. Ohsawa, T.; Takagaki, T.; Haneda, A.; Oishi, T., Tetrahedron Lett. 1981,
18. Barbulescu, N.; Cuza, O.; Barbulescu, E.; Moya-Gheorghe, S.; Zavoranu,
2583.
D., Rev. Roum. Chem. 1985, 36, 295 (Chem. Abstr. 1985, 103, 123 042t).
54. (a) Gassman, P. G.; Pape, P. G., J. Org. Chem. 1964, 29, 160. (b) Gassman,
19. Lycan, W. H.; Puntambeker, S. V.; Marvel, C. S., Org. Synth., Coll. Vol.
P. G.; Marshall, J. L., Org. Synth., Coll. Vol. 1973, 5, 424.
1943, 2, 318.
55. (a) Chou, T. C.; Chuang, K.-S.; Lin, C.-T., J. Org. Chem. 1988, 53, 5168.
20. Chen, S.-C., Synthesis 1974, 691.
(b) Hales, N. J.; Heaney, H.; Hollinshead, J. H., Synthesis 1975, 707.
(c) Hales, N. J.; Heaney, H.; Hollinshead, J. H.; Singh, P., Org. Synth.,
21. Ordubadi, M. D.; Pekhk, T. I.; Belikova, N. A.; Rakhmanchik, T. M.;
Coll. Vol. 1988, 6, 82.
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