SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE 1

Sodium Bis(2-methoxyethoxy)aluminum Phosphate esters afford the alcohol.4 Some epoxides can be
Hydride1,2 reduced to the alcohol (temperatures above 0 ◦ C are required).
Disulfides give thiols while sulfoxides yield sulfides. Sulfones
are generally inert or give low yields of sulfides. Haloalkanes,
NaAlH2(OCH2CH2OMe)2 haloarenes, and organosilicon halides undergo hydrogenolysis to
the alkane, arene, and silane, respectively.5 Benzylic aldehydes
[22722-98-1] C6 H16 AlNaO4 (MW 202.19) or alcohols, aryl alkyl or diaryl ketones, and aryl acids conta-
InChI = 1/2C3H7O2.Al.Na.2H/c2*1-5-3-2-4;;;;/h2*2-3H2, ining strong electron donating groups in the ortho or para
1H3;;;;/q2*-1;2*+1;;/rC6H16AlO4.Na/c1-8-3-5-10-7- position also undergo hydrogenolysis at 120–140 ◦ C.6 Acetals are
11-6-4-9-2;/h3-7H2,1-2H3;/q-1;+1 usually stable toward hydrogenolysis or elimination at 0–20 ◦ C,
InChIKey = XJIQVZMZXHEYOY-QHUCNSMPAR except in the presence of a conjugated double bond and bromide
(eq 1)17a or in certain quinone monoacetal systems.10b
(reducing agent for many functional groups;1 methylation reagent
for aryl-activated compounds;19 can function as a base;21 can Partial Reductions. Low-temperature conditions or the use
hydroaluminate alkenes and alkynes22 ) of alcohol or amine-modified SMEAH have proven especially
valuable for partial functional group reductions.1,2 Carboxylic
Alternate Name: SMEAH, Red-Al® , Vitride. esters, nitriles, and amides can be reduced to the aldehyde at
Physical Data: fp 4 ◦ C (3.4 M toluene solution); d 1.036 g cm−3 low temperatures. The morpholine or N-methylpiperazine mod-
(3.4 M toluene solution), d 1.122 g cm−3 (solid); highly viscous ified reagent also yields aldehydes at −55 to 0 ◦ C.8,9 Lactones
liquid at rt; thermally stable up to 205 ◦ C, upon which vigorous are converted to lactols by unmodified SMEAH at −70 ◦ C2b or
decomposition starts. with the EtOH, pyridine, or i-PrOH modified reagent at 0 ◦ C.
Solubility: sol aromatic hydrocarbons, ether, THF, DME; insol N-Substituted cyclic imides provide hydroxylactams upon reduc-
aliphatic hydrocarbons. tion at −78 ◦ C.14 It is the reagent of choice for the reduction of
Form Supplied in: 3.4 M solution in toluene. 145 g contains Cp2 ZrCl2 to Cp2 ZrClH.11
1 mol of active hydride. The pure compound is a slightly yellow,
glassy solid. Me Me
N N
Analysis of Reagent Purity: concentration can be determined SMEAH, PhH
Br rt
by iodometric titration. The titration of SMEAH solutions can (1)
be performed using salicylaldehyde phenyl hydrazone,24 using 75%

9H-fluoren-9-one,25 or by NMR spectroscopy, using the No-D

1 H NMR-based method.26 O OMe O
MeO OMe MeO OMe
Handling, Storage, and Precautions: highly flammable; mois-
ture sensitive; reacts less strongly with H2 O than LiAlH4 ; potent
skin irritant. Use in a fume hood. Selective Reductions. Vinylogous amides have been selec-
tively reduced to the β-ketoamine (eq 2).12a SMEAH is superior
to LiAlH4 for the reduction of acetal-protected cyanohydrins to
the aldehyde.12b It chemoselectively reduces α-formyl ketones to
Original Commentary the α-hydroxymethyl ketone.12c Lactones are stable in the pres-
ence of ketone or aldehyde functionality at low temperatures.
Melinda Gugelchuk SMEAH modified by alcohols or in pyridine solvent selectively
University of Waterloo, Waterloo, Ontario, Canada reduces lactones in the presence of an amide or ester.13a Ester
groups in amidoesters undergo selective reduction at 0 ◦ C and
Functional Group Reductions. SMEAH has reducing proper- short reaction times.13b SMEAH gives higher yields than LiAlH4
ties fully comparable to Lithium Aluminum Hydride, making in the reduction of some hydroxy-substituted carbonyl compounds
it a valuable alternative reducing reagent.1,6 Some practical (eq 3).13c 5,5-Disubstituted hydantoins are selectively reduced at
advantages of SMEAH are that it does not ignite when exposed the 4-position13d and keto aldehydes have been cleanly reduced to
to moist air or O2 , has greater solubility in aromatic solvents and the keto alcohol.13e Optically active α-alkoxy carboxamides have
ethers, and reactions can be carried out at higher temperatures (up been reduced to the α-alkoxy aldehydes without racemization.13f
to 200 ◦ C). Carboxylic esters, acids, acid chlorides, anhydrides,
aldehydes, and ketones are efficiently converted to the alcohol. SMEAH
O PhH or Et2O
O
Cyclic anhydrides and lactones yield diols. Carboxylic esters are R1
–5 to 5 °C R1
not reduced at −78 ◦ C and t-Bu and Ph esters are generally stable N
10–55%
N (2)
R2 R2
to SMEAH at low temperature.
Nitriles, amides, imines, azido compounds, nitro compounds, SMEAH
HO CO2Et HO Me
isocyanates, urethanes, sulfonamides, oximes, lactams, and N THF, toluene N
(3)
imides can be reduced to the amine. The formation of aziridines N reflux, 18 h N
CO2Et 80% Me
can complete with simple reduction of ketoximes and their O-alkyl
derivatives. Nitroarenes form azoxyarenes, azoarenes, or hydra-
zoarenes depending on reaction conditions.3
1,2- vs. 1,4-Reductions. The structure of the enone, solvent,
Alkanesulfonates can be converted to alkanes or to alcohols.
relative initial concentrations, temperature, and softness or hard-

Avoid Skin Contact with All Reagents

2 SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE

ness of the hydride reagent all play a role in controlling the mode Methylation Reagent. The reduction of aryl-conjugated
of addition to enone systems. SMEAH typically acts as a hard double bonds yields selective methylation at the more highly
hydride, favoring 1,2-addition in these reactions. High yields of arylated carbon atom.19 The Me group originates from the
the allylic alcohol have been reported by inverse addition of the hydride OMe group. Aryl-activated alkanes undergo methylation
hydride to aliphatic or alicyclic α,β-unsaturated aldehydes and by this reagent. Diaryl and condensed aromatic ketones undergo
esters.14a,b It favors 1,2-addition to cyclic α-enones and is the hydrogenolysis and subsequent methylation at the benzylic
reagent of choice for the low-temperature reduction of enol esters carbon.
of alicyclic 1,3-diketones (eq 4).18c Alkyl esters are not reduced
under these conditions. The SMEAH/CuBr/2-butanol reagent is Reductive Cleavage of Ethers. Ethers are usually stable at
extremely efficient for 1,4-reduction.15 Nitrile and ester functions temperatures below 100 ◦ C. At higher temperatures, cleavage of
are stable under the conditions of the conjugate reduction, while the ether linkage occurs. SMEAH is a useful reagent for debenzy-
aldehydes, ketones, and bromides are attacked by the complex. lation and deallylation of aryl benzyl and aryl allyl ethers (eq 7).20
The reaction is enhanced by a vicinal methoxy group. This method
O O is recommended for debenzylation and deallylation of phenolic
1. SMEAH, THF, –78 °C
R 2. H3O+ R ethers that are labile to acid or catalytic hydrogenolysis.
(4)
60%
HO OR′ HO SMEAH, xylene
R = (CH2)6CO2Me reflux, 10 h
(7)
R′ = i-Pr, PhCO, ArSO2 BnO 66% HO
OMe OMe

Stereoselective Reductions. The stereochemistry of reduc-

tions often varies, depending on the solvent. A possible factor is Use as a Base. SMEAH can act as a strong base. It is known
the degree of solvation. In some cases, complete reversal of stereo- to promote isomerization and dehydrogenation of aromatic
chemistry has been observed by using SMEAH in benzene versus hydrocarbons by a base-catalyzed reaction.21a,b The Stevens
THF.1 In comparison to other reducing agents, SMEAH often rearrangement of berbine methiodide affords the spiroisoquino-
shows stereoselectivity opposite to that of LiAlH4 , Sodium Boro- line derivative in high yield.21c
hydride, or lithium trialkoxyaluminum hydrides. Unsymmetrical
epoxides are attacked preferentially at the least-substituted car- Hydroalumination Reagent. Double and triple bonds
bon atom to give the more highly substituted alcohol as the major undergo catalytic hydroalumination with a number of aluminum
product.16 Exceptionally high regioselectivity in the reduction of hydride reagents.22 The effectiveness of SMEAH in this reaction
α,β-epoxy alcohols to the 1,3-diol has been observed (eq 5).16b–e is comparable to that of LiAlH4 , NaAlH4 , NaAlHMe3 , LiAlH2
Substituents at the α-carbon reverses the selectivity and decreases (NR2 )2 , or NaAlH2 (NR2 )2 .
the reaction rate. The reduction of α-silyloxy ketones produces
syn-vicinal diols with high levels of diastereoselectivity.16f,g

SMEAH, THF
O 0 °C R OH
(5)
First Update
R OH 82–98%
OH Luiz F. Silva, Jr., Ramon S. Vasconcelos & Samir A. P. Quintiliano
Universidade de São Paulo, São Paulo, Brazil
SMEAH reacts with bridged bicyclic ketones from the less
hindered side of the carbonyl.17a Reduction of gem-dihalocyclo- Reduction of Carboxylic Acids and Derivatives. SMEAH is
propanes gives anti-monohalides as the major product.17b It commonly used in preference to other hydrides for the reduction
reduces α-alkynic alcohols to trans-allylic alcohols with high of esters because of its ease of use. Moreover, a higher efficiency
selectivity.18a–d Alkynyl ethers give almost exclusively O-alkyl was observed during the reduction of an ester to the corresponding
enol ethers with the (E) configuration with SMEAH, but with alcohol on a scale of 10 kg.27 The reduction of esters can be per-
alcohol-modified SMEAH reagent (Z)-enol ethers are obtained formed in the presence of several functional groups. Examples are
(eq 6).18e the reduction of a bromo-ester,28 of a sensitive peroxy-containing
ester (eq 8),29 and of esters in the presence of nitriles.30 However,
4 equiv SMEAH a triisopropylsilyl enol ether was cleaved during the reduction of
R1O
THF, reflux tert-butyl esters.31 Bulky alkyl carboxylates bearing an α-fluorine
62–93%
R atom are reduced by SMEAH.32 Malonate sodium salts are also
R1O R (6) reduced.33 SMEAH is used for the deprotection of alcohols, such
8 equiv SMEAH as acetates, benzoates, and pivaloates. Acetyl groups can be
R2OH, THF, reflux
R1O R selectively removed in the presence of tert-butyl esters.34 In
72–83%
the synthesis of taxoids, selective deprotections of alcohols were
R = alkyl developed to remove C-2 benzoates,35 C-436 and C-1337 acetates,
R1, R2 = alkyl, alicyclic and C-5 O-cinnamoyl esters.38

A list of General Abbreviations appears on the front Endpapers

 SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE 3

CO2Et
1.5 equiv SMEAH (65% in toluene) tion reaction may occur during the reduction of imides65 and of
THF, 0 °C to rt, 2.3 h
carbamates.66 The reduction of carbamates is also useful in the
48%
O O O (7% of sm)
synthesis of alkylamines. Under the conditions required for such a
transformation, the reduction of carbon–chloride bonds may take
OH place.67 The reduction of nitriles leads either to amines68 or to
(8) aldehydes.69 The amine formed in the reaction can further react
O O O with a carbonyl group, forming a new ring.70

HO OH 1. 4.8 equiv SMEAH (70% in toluene),

Esters give aldehydes using SMEAH treated with amines39 THF, reflux, 1 h
O 2. (PhO)2P(O)N3, Ph3P,
or with pyrrolidine/potassium tert-butoxide.40 Diesters can be EtO2CN=NCO2Et, THF
transformed either into the monoalcohol ester41 or into the BnN 92%
dialdehyde.39 Treatment of alkyl benzoates42 and of benzoic NBn
acid43 derivatives with SMEAH may give toluene derivatives. O N3 N3
Carboxylic acids are selectively reduced to primary alcohols in
the presence of oxazolidinones44 and of carbamates.45
The reduction of amides to amines can be performed chemo-
selectively in the presence of epoxides, of RNHTS46 and of (10)
RNHBoc47 groups. Likewise esters and amides, including N O N
Weinreb amides,48 can be reduced to aldehydes.49 Besides alde- Bn H H Bn
hydes and amines, the reduction of amides can lead to imines.
Sulfonamide protecting groups, such as tosyl50 and mesyl,51 can
be cleaved from a wide variety of amines.52 In some cases, this Reduction of Ketones and of Aldehydes. The reduction of
reductive cleavage is followed by a cyclization reaction (eq 9).52 ketones and of aldehydes can be performed in the presence of car-
Presumably, ester groups are reduced under the conditions boxylic acids, esters, nitriles, carbamates, alkynes, and halides.
required for the deprotection of the amines.52 The chlorosulfonyl The reaction conditions can be adjusted to reduce an aldehyde
group is removed from lactams using SMEAH.53 The N-triflate in the presence of a ketone moiety.71 The alkoxide formed during
bond is also cleaved.54 the reduction can participate in cyclization reactions.72 Remark-
ably, the SMEAH-promoted reduction of acyclic ketones and
OH aldehydes can be diastereoselective (eq 11).73 In addition, the
O Ph diastereomer formed can be different from that obtained with
6.8 equiv SMEAH (70% in toluene)
o-xylene, reflux, 35 min other hydride reagents.74 In cyclic systems, diastereoselective
O O
reductions are observed in a wide variety of carbocyclic and het-
91%
O erocyclic systems, including five-,75 six- (eq 12),76 seven-,77 and
NTs
eight-membered78 rings. Aryl ketones are reduced to the
O Ph corresponding alkane.79
O O (9)
Ph Ph
3.0 equiv SMEAH (65% in toluene)
O N
O toluene, –78 °C OH (11)
93%
Lactones can be reduced either to diols or to lactols depending Ph NH2 Ph NH2
on the reaction conditions. In the reduction of substituted lactones,
the hydride is delivered preferentially from one of the faces giving
lactols in a diastereoselective manner.55 The reduction of N
1.3 equiv SMEAH (0.05 M in THF)
anhydrides affords lactones and/or hydroxy-carboxylic acids. The MeO AlCl3, THF, –20 °C
reduction of unsymmetrical cyclic anhydrides may occur with OH Et 50%
good selectivity.56 An efficient method to obtain cyclic amines N O
is the reduction of the corresponding lactams with SMEAH.57 Me CO2Me
Under these conditions, the reduction of carboxylic acids, esters,
N
lactones, and lactols also take place, as expected.57 However, the
MeO (12)
reduction of lactams can be performed without the reductive cleav-
age of N–Ts bonds.58 In the presence of an internal nucleophile, OH Et
N
a cyclization occurs during the reduction (eq 10).59 The reduction OH
of chiral bicyclic lactams to carbinolamines is an important step Me CO2Me
in the synthesis of enantiomerically pure compounds.60 Lactams
can be transformed into iminium ions.61
Imides can be reduced either to amines62 or to aldehydes63 β -Unsaturated Compounds. The reduction
Reduction of α ,β
depending on the reaction conditions and on the structure of the of α,β-unsaturated aldehydes, -ketones, and -esters gives allylic
substrate. The reduction of N–Ts and of C–F bonds may occur alcohols. The 1,2-hydride addition at unsaturated ketones usually
during the reduction of imides.64 Similar to lactams, a cycliza- occurs with a good level of diastereoselectivity either in cyclic80

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4 SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE

(eq 13) or in acyclic81 systems (eq 14). For conjugated esters, cyclization took place.96 The reduction of 4-silyloxy propargylic
the reduction can be carried out in the presence of lactones82 alcohols gives a 1,3-silyl migration product.97
and of carbamates.83 The reduction of α,β-unsaturated ketones
to the corresponding saturated compound was performed in the OH 2.0 equiv SMEAH (65% in toluene)
presence of esters, using a mixture of SMEAH, CuBr, and THF, –72 °C, 25 min
2-butanol.84 Conjugated double bonds are selectively reduced 80%
in the presence of a nonconjugated one.85 Treatment of O CO2Me
α,β-unsaturated esters with SMEAH may give either a saturated OH
ester86 or a saturated alcohol.87 Saturated cyclic amines are (16)
obtained from α,β-unsaturated lactams. Nitrostyrene furnishes CO2Me
a saturated amine.88 The reduction of N-alkylpyridones gives O
enaminones.89 The reduction of α,β-unsaturated silylimines
yields silylamines diastereoselectively.90 The reduction of propargylic alcohols can also be quenched
with other electrophiles, besides a proton source, such as
0.7 equiv SMEAH, 0.5 equiv NaI
iodine, NIS, NCS,98 tributylstannyl chloride,99 and phenyl
toluene, t-BuOMe, –30 °C, 5 h sulfenyl chloride.100 Propargylic ketones are reduced to E-allylic
TBSO O 71% alcohols.101 The hydroalumination of trifluoromethylated alkynes
gives E-alkenes.102 Allenes are formed in the reaction of propargyl
(13)
chlorides (eq 17).103
TBSO OH + TBSO OH
32:1 OH
Cl 3.0 equiv SMEAH (65% in toluene)
TIPS Et2O, –30 to –20 °C, 6 h
2.5 equiv SMEAH (65% in toluene) TIPS 70%
O S toluene, –78 °C, 1 h OH Cl
80% OH
TBSO S
TIPS (17)

OH S TIPS
(14) OH
TBSO S

Homopropargylic alcohols are reduced to E-alkenes (eq 18).104

SMEAH is used as a hydride source promoting either the
Reduction of Alkenes and Alkynes. The stereoselective hydrometalation in the presence of Cp2 TiCl2 or the hydrogenation
reduction of propargylic alcohols giving E-alkenes is accelerated of olefins in the presence of ZnCl2 .105 Aromatic compounds are
by the presence of phenyl-substituted silyl groups, allowing the also reduced under similar conditions. In the presence of an alco-
selective reduction of an alkyne in the presence of other triple hol, such as methanol, the reduction of acetylenic ethers furnishes
bonds (eq 15).4 Boc-protected propargylamines are reduced to Z-alkenes.106
E-alkenes.91
TMS 1.2 equiv SMEAH (70% in toluene)
OH THF, –20 °C to rt, 30 min
1.1 equiv SMEAH (1.5 M in toluene) 79%
toluene, 0 °C, 1 h OH
TPS 81%
TMS
TMS OH (18)
OH
TPS (15)

Reductive Ring Opening of Epoxides. The hydroxyl-directed

TMS
regio- and stereoselective ring opening of 2,3-epoxy alcohols
mediated by SMEAH is an efficient method for the synthesis of
Propargylic alcohols are reduced even in the presence of 1,3-diols. Thiiranes107 and aziridines108 react in a similar fashion.
epoxides.92 Moreover, RNHBoc groups usually survive the However, 1,2-diols are obtained from 2-fluoro-109 and from
reductive reaction conditions,91 albeit cyclization reactions 3-(tributylstannyl)-2,3-epoxy alcohols.110 The reduction of
between the hydroxyl group and the carbamate can take place.93 2,3-epoxy alcohols bearing a suitably positioned ester leads to the
However, alcohol protecting groups, such as acetates, pivaloates, formation of a cyclic ether formed by the attack of the alkoxide
and benzoates, are usually cleaved.94 On the other hand, originated by the reduction of ester to the epoxide.111 The for-
γ-hydroxy-α,β-acetylenic esters give E-γ-hydroxy-α,β-alkenoic mation of 1,2-diols is observed for sugar derivatives bearing a
esters (eq 16).95 When a cyclic tetrayne alcohol, bearing a propar- 3-hydroxy-1-phenyl-1,2-epoxide unit.112 The reduction of
gylic moiety, was treated with SMEAH, a transannular reductive α,β-epoxy-ketones113 and -aldehydes114 gives 1,3-diols. The

A list of General Abbreviations appears on the front Endpapers

 SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE 5

regioselective ring opening of α,β-epoxy amides occurs with a The reductive cleavage of phosphates mediated by SMEAH is
crown ether (eq 19).115 used in the resolution of binaphtol derivatives.131 Phosphorus
chlorides are reduced to the corresponding phosphino
O compounds.132 The reaction of phospholanes with SMEAH gives
1.2 equiv SMEAH (70% in toluene)
O an anion, which can be reacted with alkyl halides, forming a P–C
Me 1.2 equiv [15]crown, DME, –40 °C to rt
N bond (eq 23).133
80%
H
Me
OH O Ph 10 equiv SMEAH (65% in toluene)
N toluene, reflux, 20 h
Me (19) SMe
N 42%
O N N
H H Me
Ph N
The reaction of 3,4-epoxy alcohols yields the corresponding (22)
1,4-diol with moderate to very good regioselectivity (eq 20).116 O N N
The corresponding aziridines react similarly, giving 1,4-amino H
alcohols derivatives.116 The reductive ring opening occurs with a
good level of regioselectivity in the reduction of epoxides at either
1. 4.0 equiv SMEAH (65% in toluene)
tetrahydronaphthalenes117 or at cyclopentanes.118 THF, rt, 1 h
2. 16 equiv MeI, 0 °C, 5 min
3.0 equiv SMEAH (70% in toluene) Ph Ph
P 51%
O THF, –78 °C to rt, 4 d
OH O OMe
R 95%
+ (23)
OH Ph P Ph
OH Me Me
OH + R
R (20)
OH
R = Et: 92:8
Halides. SMEAH promotes the reduction of carbon–halide
R = Ph: 70:30
bonds to the corresponding carbon–hydrogen bond. Vinyl difluo-
rides are converted to the monofluoro E-alkenes (eq 24).134 Mono-
Nitrogen Compounds. The reaction of N-benzoyl hydrazones halopyridines are dehalogenated using Cp2 TiCl2 /SMEAH.135
with SMEAH gives hydrazines. Under this condition, the es- OMEM
ter group is converted to the alcohol (eq 21).119 The delivery 3.8 equiv SMEAH (65% in toluene)
F pentane, reflux, 3 h
of the hydride in the reduction of aziridines occurs at the less-
79%
substituted carbon.120 Azides are reduced to the corresponding F OH (E:Z = 9:1)
amino group.121 The reduction of nitro compounds can lead to OMEM
either amines or to azo derivatives. The N–N bond of hydrazines is (24)
reduced using SMEAH.122 SMEAH promotes the diastereoselec-
tive reduction of imines123 and of β-hydroxy oximes124 to amines F OH
and alkoxy amino alcohols, respectively. Alkoxy amines124 are
converted to amines and oximes are transformed into aziridines.125
Metal Complexes. Treatment with SMEAH affords metal
The reduction of 2-pyridones is mediated by SMEAH.126
hydrides from metal complexes of the general structure Lm MXn ,
where L is a ligand, M is a metal (Fe, Co, Cr, Mn, Mo, W, V,
OTBS
4.0 equiv SMEAH (65% in toluene) Rh, Nb, Zr, Ta, Ir, Ru, Os), and X is a halide or a carboxylate.136
CO2t-Bu toluene, 0 °C, 2 h
Ph The Schwartz reagent (Cp2 Zr(H)Cl) is prepared in situ from a cat-
N
60% alytic amount of Cp2 ZrCl2 and SMEAH.137 Cationic complexes,
syn:anti = 1:1
BzHN such as [Ru(η6 -C6 Me6 )(η6 -C16 H16 )][BF4 ]2 are reduced to the
OTBS neutral ones, such as [Ru(η4 -3,6-C6 Me6 H2 )(η6 -C16 H16 )].138 This
Ph OH (21) reduction also occurs with Os and Ir. Dichlorogallane (HGaCl2 ) is
prepared in situ by addition of SMEAH to gallium trichloride.139
NH
BzHN
Miscellaneous. The reduction of α,β-epoxy peroxy esters
gives α,β-epoxy aldehydes (eq 25).140 Benzyl-protected allyl
Sulfur and Phosphorus Compounds. The reduction of alcohols containing a suitably positioned hydroxyl group for metal
2-(methylthio)imidazole yields an imidazole derivative (eq 22).127 complexation are prone to reductive cleavage of the benzyloxy
Aromatic diamines are obtained from benzothiadiazole.128 group through an SN 2 hydride delivery.141 SMEAH activates
SMEAH can be used as a hydride source to quench sulfur- magnesium and zinc surfaces, removing moisture, alcohols, and
stabilized carbocations, giving dithioacetals.129 Phosphinates and peroxides from the metal.142 SMEAH initiates the polymeriza-
phosphonates are reduced to phosphinite and to phosphino com- tion of lactides, lactams, and acrylonitrile. The dehydrocoupling
pounds, respectively, mainly in the synthesis of phosphasugars.130 of n-Bu3 SnH and n-Bu2 SnH2 , producing dimers, oligostannanes,

Avoid Skin Contact with All Reagents

6 SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE

and polystannane in the presence of transition metal complexes, is 17. (a) Kanazawa, R.; Kotsuki, H.; Tokoroyama, T., Tetrahedron Lett. 1975,
promoted by SMEAH.143 In addition, the dehydropolymerization 3651. (b) Weiss, B., Chem. Phys. Lipids 1977, 19, 347. (c) Kornet, M.
of arylsilanes and alkylsilanes affords polysilanes.143,144 J., J. Heterocycl. Chem. 1990, 27, 2125. (d) Marquez, V. E.; Twanmoh,
L.-M.; Wood, H. B., Jr.; Driscoll, J. S., J. Org. Chem. 1972, 37, 2558.
(e) Murphy, R.; Prager, R. H., Angew. Chem., Int. Ed. Engl. 1976, 29,
0.5 equiv SMEAH (0.8 M in toluene) 617. (f) Kobayashi, Y.; Takase, M.; Ito, Y.; Terashima, S., Bull. Chem.
O
O toluene, –78 °C, 2 h Soc. Jpn. 1989, 62, 3038.
Ph OO-t-Bu 70% 18. (a) Bartlett, P. A.; Johnson, W. S., J. Am. Chem. Soc. 1973, 95, 7501.
(b) Traas, P. C.; Boellens, H.; Takken, H. J., Recl. Trav. Chim. Pays-Bas
O 1976, 95, 57. (c) Sih, C. J.; Heather, J. B.; Peruzzotti, G. P.; Price, P.;
O (25)
Sood, R.; Lee, L. F. H., J. Am. Chem. Soc. 1973, 95, 1676.
Ph H
19. (a) Semmelhack, M. F.; Stauffer, R. D.; Yamashita, Y., J. Org. Chem.
Related Reagents. Copper(I) Bromide–Sodium Bis(2-metho- 1977, 42, 3180. (b) Semmelhack, M. F.; Stauffer, R. D., J. Org. Chem.
1975, 40, 3619.
xyethoxy)aluminum Hydride. SMEAH/CuBr/2-butanol; Sch-
20. (a) Jones, T. K.; Peet, J. H. J., Chem. Ind. (London) 1971, 995. (b) Ma,
wartz reagent (Cp2 Zr(H)Cl); Dichlorogallane (HGaCl2 ).
P.; Martin, V. S.; Masamune, S.; Sharpless, K. B.; Viti, S. M., J. Org.
Chem. 1982, 47, 1378. (c) Viti, S. M., Tetrahedron Lett. 1982, 23, 4541.
(d) Minami, N.; Ko, S. S.; Kishi, Y., J. Am. Chem. Soc. 1982, 104, 1109.
1. (a) Malek, J., Org. React. 1988, 36, 249. (b) Malek, J., Org. React. (e) Finan, J. M.; Kishi, Y., Tetrahedron Lett. 1982, 23, 2719. (f) Nakata,
1985, 34, 1. (c) Vit, J., Eastman Org. Chem. Bull. 1970, 42, 1. T.; Tanaka, T.; Oishi, T., Tetrahedron Lett. 1983, 24, 2653. (g) Nakata,
2. Seyden-Penne, J. Reductions by the Alumino- and Borohydrides in T.; Fukui, M.; Ohtsuka, H.; Oishi, T., Tetrahedron 1984, 40, 2225.
Organic Synthesis; 2nd ed.; Wiley-VCH: New York, 1997. 21. (a) Sydnes, L.; Skattebøl, L., Tetrahedron Lett. 1974, 3703. (b) Sydnes,
3. Love, B. E.; Jones, E. G., J., Org. Chem. 1999, 64, 3755. L. K.; Skattebøl, L., Acta Chem. Scand. (B) 1978, 32, 632. (c) Miyano,
4. Igawa, K.; Tomooka, K., Angew. Chem. Int. Ed. 2006, 45, 232. S.; Hashimoto, H., Bull. Chem. Soc. Jpn. 1975, 48, 3665.
5. Hoye, T. R.; Aspaas, A. W.; Eklov, B. M.; Ryba, T. D., Org. Lett. 2005, 22. (a) Jones, T. K.; Denmark, S. E., Org. Synth. 1986, 64, 182. (b) Trost, B.
7, 2205. M.; Lautens, M., J. Am. Chem. Soc. 1987, 109, 1469. (c) Chan, K.-K.;
Cohen, N.; De Noble, J. P.; Specian, A. C., Jr.; Saucy, G., J. Org. Chem.
6. (a) Capka, M.; Chvalovsky, V.; Kochloefl, K.; Kraus, M., Collect.
1976, 41, 3497. (d) Mayer, H. J.; Rigassi, N.; Schwieter, U.; Weedon, B.
Czech. Chem. Commun. 1969, 34, 118. (b) Cerny, M.; Malek, J.; Capka,
C. L., Helv. Chim. Acta 1976, 59, 1424. (e) Sola, L.; Castro, J.; Moyano,
M.; Chvalovsky, V., Collect. Czech. Chem. Commun. 1969, 34, 1025.
A.; Pericas, M.; Riera, A., Tetrahedron Lett. 1992, 33, 2863.
(c) Kumar, V.; Remers, W. A., J. Med. Chem. 1979, 22, 432. (d) Bazant,
V.; Capka, M.; Cerny, M.; Chvalovsky, V.; Kochloefl, K.; Kraus, M.; 23. (a) Cerny, M.; Malek, J., Tetrahedron Lett. 1972, 691. (b) Malek, J.;
Malek, J., Tetrahedron Lett. 1968, 3303. (e) Malek, J.; Cerny, M., Cerny, M., J. Organomet. Chem. 1975, 84, 139. (c) Cerny, M.; Makel,
Synthesis 1972, 217. J., Collect. Czech. Chem. Commun. 1976, 41, 119.
7. (a) Corbett, J. F., J. Chem. Soc., Chem. Commun. 1968, 1257. (b) Kraus, 24. Kametani, T.; Huang, S.-P.; Ihara, M.; Fukumoto, K., J. Org. Chem.
M.; Kochloefl, K., Collect. Czech. Chem. Commun. 1969, 34, 1823. 1976, 41, 2545.
(c) Barclay, L. R. C.; McMaster, I. T.; Burgess, J. K., Tetrahedron Lett. 25. (a) Hilscher, J.-C., Chem. Ber. 1975, 108, 727. (b) Minabe, M.; Suzuki,
1973, 3947. K., Bull. Chem. Soc. Jpn. 1975, 48, 1480. (c) Kametani, T.; Huang,
8. Truesdale, L. K., Org. Synth. 1989, 67, 13. S.-P.; Koseki, C.; Ihara, M.; Fukumoto, K., J. Org. Chem. 1977, 42,
3040.
9. (a) Capka, M.; Chvalovsky, V., Collect. Czech. Chem. Commun. 1969,
34, 2782; 3110. (b) Barton, T. J.; Kippenhan, R. C., Jr., J. Org. Chem. 26. Ashby, E. C.; Noding, S. A., J. Org. Chem. 1980, 45, 1035.
1972, 37, 4194. (c) Kraus, M., Collect. Czech. Chem. Commun. 1972, 27. Srinivas, K.; Srinivasan, N.; Reddy, K. S.; Ramakrishna, M.; Reddy,
37, 3052. C. R.; Arunagiri, M.; Kumari, R. L.; Venkataraman, S.; Mathad, V. T.,
10. (a) Cerny, M.; Malek, J., Tetrahedron Lett. 1969, 1739. (b) Cohen, Org. Process Res. Dev. 2005, 9, 314.
N.; Lopresti, R. J.; Saucy, G., J. Am. Chem. Soc. 1979, 101, 6710. 28. Wells, A., Synth. Commun. 1996, 26, 1143.
(c) Cerny, M.; Malek, J., Collect. Czech. Chem. Commun. 1970, 35, 29. Jin, H.-X.; Liu, H.-H.; Zhang, Q.; Wu, Y., J. Org. Chem. 2005, 70, 4240.
1216; 2030; 3079. (d) Pawson, B. A.; Chan, K.-K.; DeNoble, J.; Han,
30. Hu, Y.; Wittmer, L. L.; Kalkbrenner, M.; Evers, A. S.; Zorumski, C. F.;
R.-J. L.; Piermattie, V.; Specian, A. C.; Srisethnil, S.; Trown, P. W.;
Covey, D. F., J. Chem. Soc., Perkin Trans. 1 1997, 3665.
Bohoslawec, O.; Machlin, L. J.; Gabriel, E., J. Med. Chem. 1979, 22,
1059. 31. Myers, A. G.; Siu, M.; Ren, F., J. Am. Chem. Soc. 2002, 124, 4230.
11. Fleischhacker, W.; Markut, H., Monatsh. Chem. 1971, 102, 569; 587. 32. Ihara, M.; Kawabuchi, T.; Tokunaga, Y.; Fukumoto; Keiichiro,
Tetrahedron: Asymmetry 1994, 5, 1041.
12. (a) Kanazawa, R.; Tokoroyama, T Synthesis 1976, 526. (b) Bartsch,
H.; Schwarz, O., J. Heterocycl. Chem. 1982, 19, 1189. (c) Kompis, I.; 33. Prasad, K.; Estermann, H.; Chen, C. P.; Repic, O.; Hardtmann, G. E.,
Wick, A., Helv. Chim. Acta 1977, 60, 3025. Tetrahedron: Asymmetry 1990, 1, 421.
13. (a) Stibor, I.; Janda, M.; Srogl, J., Z. Chem. 1970, 10, 342. (b) Böhme, 34. Banfi, L.; Basso, A.; Guanti, G.; Zannetti, M. T., Tetrahedron:
H.; Sutoyo, P. N., Liebigs Ann. Chem. 1982, 1643. (c) Sone, T.; Asymmetry 1997, 8, 4079.
Terashima, S.; Yamada, S.-I., Chem. Pharm. Bull. 1976, 24, 1273. (d) 35. Chen, S.-H.; Farina, V.; Wei, J.-M.; Long, B.; Fairchild, C.; Mamber,
Hayashi, M.; Terashima, S.; Koga, K., Tetrahedron 1981, 37, 2797. S. W.; Kadow, J. F.; Vyas, D.; Doyle, T. W., Bioorg. Med. Chem. Lett.
(e) Terashima, S.; Hayashi, M.; Koga, K., Tetrahedron Lett. 1980, 21, 1994, 4, 479.
2733. 36. Chen, S.-H.; Kadow, J. F.; Farina, V.; Fairchild, C. R.; Johnston, K. A.,
14. (a) Mukaiyama, T.; Yamashita, H.; Asami, M., Chem. Lett. 1983, 385. J. Org. Chem. 1994, 59, 6156.
(b) Speckamp, W. N.; Hiemstra, H., Tetrahedron 1985, 41, 4367. 37. Kingston, D. G. I.; Chordia, M. D.; Jagtap, P. G.; Liang, J.; Shen, Y.-C.;
15. Hart, D. W.; Schwartz, J., J. Am. Chem. Soc. 1974, 96, 8115. Long, B. H.; Fairchild, C. R.; Johnston, K. A., J. Org. Chem. 1999, 64,
16. (a) Weselowsky, V. W.; Moiseenkov, A. M., Synthesis 1974, 58. 1814.
(b) Schlosser, M.; Brich, Z., Helv. Chim. Acta 1978, 61, 1903. (c) Corey, 38. Sako, M.; Suzuki, H.; Yamamoto, N.; Hirota, K.; Maki, Y., J. Chem.
E. J.; Smith, J. G., J. Am. Chem. Soc. 1979, 101, 1038. Soc., Perkin Trans. 1 1998, 417.

A list of General Abbreviations appears on the front Endpapers

 SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE 7

39. Hagiya, K.; Mitsui, S.; Taguchi, H., Synthesis 2003, 823. 75. Dimitroff, M.; Fallis, A. G., Tetrahedron Lett. 1998, 39, 2531.
40. Abe, T.; Haga, T.; Negi, S.; Morita, Y.; Takayanagi, K.; Hamamura, K., 76. Choi, Y. G.; Ishikawa, H.; Velcicky, J.; Elliott, G. I.; Miller, M. M.;
Tetrahedron 2001, 57, 2701. Boger, D. L., Org. Lett. 2005, 7, 4539.
41. Ladouceur, G. H.; Cook, J. H.; Doherty, E. M.; Schoen, W. R.; 77. Cid, J.; Alonso, J. M.; Andres, J. I.; Fernandez, J.; Gil, P.; Iturrino, L.;
MacDougall, M. L.; Livingston, J. N., Bioorg. Med. Chem. Lett. 2002, Matesanz, E.; Meert, T. F.; Megens, A.; Sipido, V. K.; Trabanco, A. A.,
12, 461. Bioorg. Med. Chem. Lett. 2004, 14, 2765.
42. Boers, R. B.; Randulfe, Y. P.; van der Haas, H. N. S; van Rossum-Baan, 78. Holton, R. A.; Somoza, C.; Kim, H. B.; Liang, F.; Biediger, R. J.;
M.; Lugtenburg, J., Eur. J. Org. Chem. 2002, 2094. Boatman, P. D.; Shindo, M.; Smith, C. C.; Kim, S.; Nadizadeh, H.;
43. Beccalli, E. M.; Marchesini, A.; Pilati, T., Tetrahedron 1996, 52, 3029. Suzuki, Y.; Tao, C.; Vu, P.; Tang, S.; Zhang, P.; Murthi, K. K.; Gentile,
44. Jones, D. M.; Nilsson, B.; Szelke, M., J. Org. Chem. 1993, 58, 2286. L. N.; Liu, J. H., J. Am. Chem. Soc. 1994, 116, 1597.
45. Juszczyk, P.; Kasprzykowska, R.; Kolodziejczyk, A. S., Lett. Peptide 79. Heinrich, T.; Böttcher, H.; Gericke, R.; Bartoszyk, G. D.; Anzali, S.;
Science 2004, 10, 79. Seyfried, C. A.; Greiner, H. E.; van Amsterdam, C., J. Med. Chem.
2004, 47, 4684.
46. Bon, E.; Biggs, D. C. H; Bertrand, G.; Bigg, D. C. H., J. Org. Chem.
1994, 59, 1904. 80. Curran, T. T.; Hay, D. A.; Koegel, C. P.; Evans, J. C., Tetrahedron 1997,
53, 1983.
47. Voight, E. A.; Bodenstein, M. S.; Ikemoto, N.; Kress, M. H.,
Tetrahedron Lett. 2006, 47, 1717. 81. Nicolaou, K. C.; Pihko, P. M.; Bernal, F.; Frederick, M. O.; Qian, W.;
48. Schwindt, M. A.; Belmont, D. T.; Carlson, M.; Franklin, L. C.; Uesaka, N.; Diedrichs, N.; Hinrichs, J.; Koftis, T. V.; Loizidou, E.;
Hendrickson, V. S.; Karrick, G. L.; Poe, R. W.; Sobieray, D. M.; van Petrovic, G.; Rodriquez, M.; Sarlah, D.; Zou, N., J. Am. Chem. Soc.
De Vusse, J., J. Org. Chem. 1996, 61, 9564. 2006, 128, 2244.
49. Hudlicky, T.; Tian, X.; Königsberger, K.; Maurya, R.; Rouden, J.; Fan, 82. Steel, P. G.; Mills, O. S.; Parmee, E. R.; Thomas, E. J., J. Chem. Soc.,
B., J. Am. Chem. Soc. 1996, 118, 10752. Perkin Trans. 1 1997, 391.
50. Coldham, I.; Warren, S., J. Chem. Soc., Perkin Trans. 1 1993, 1637. 83. Bösche, U.; Nubbemeyer, U., Tetrahedron 1999, 55, 6883.
51. Callaghan, O.; Lampard, C.; Kennedy, A. R.; Murphy, J. A., J. Chem. 84. Nunn, K.; Mosset, P.; Gree, R.; Saalfrank, R. W., J. Org. Chem. 1992,
Soc., Perkin Trans. 1 1999, 995. 57, 3359.
52. Ishizaki, M.; Hoshino, O.; Iitaka, Y., J. Org. Chem. 1992, 57, 7285. 85. Ghosh, A. K.; Gong, G., J. Org. Chem. 2006, 71, 1085.
53. Furman, B.; Kaluza, Z.; Chmielewski, M., J. Org. Chem. 1997, 62, 86. Kuethe, J. T.; Wong, A.; Wu, J.; Davies, I. W.; Dormer, P. G.; Welch,
3135. C. J.; Hillier, M. C.; Hughes, D. L.; Reider, P. J., J. Org. Chem. 2002,
67, 5993.
54. de la Fuente, M. C.; Pullan, S. E.; Biesmans, I.; Domínguez, D., J. Org.
Chem. 2006, 71, 3963. 87. Harmata, M.; Jones, D. E., Tetrahedron Lett. 1996, 37, 783.
55. Logothetis, T. A.; Eilitz, U.; Hiller, W.; Burger, K., Tetrahedron 1998, 88. Campos, F.; Bosch, M. P.; Guerrero, A., Tetrahedron: Asymmetry 2000,
54, 14023. 11, 2705.
56. Harada, K.; Kato, H.; Fukuyama, Y., Tetrahedron Lett. 2005, 46, 7407. 89. Albaneze-Walker, J.; Rossen, K.; Reamer, R. A.; Volante, R. P.; Reider,
57. Denmark, S. E.; Thorarensen, A.; Middleton, D. S., J. Am. Chem. Soc. P. J., Tetrahedron Lett. 1999, 40, 4917.
1996, 118, 8266. 90. Hicks, F. A.; Berk, S. C.; Buchwald, S. L., J. Org. Chem. 1996, 61,
58. Marino, J. P.; Bogdan, S.; Kimura, K. J., J. Am. Chem. Soc. 1992, 114, 2713.
5566. 91. Ripin, D. H. B.; Bourassa, D. E.; Brandt, T.; Castaldi, M. J.; Frost, H.
59. Overman, L. E.; Paone, D. V.; Stearns, B. A., J. Am. Chem. Soc. 1999, N.; Hawkins, J.; Johnson, P. J.; Massett, S. S.; Neumann, K.; Phillips,
121, 7702. J.; Raggon, J. W.; Rose, P. R.; Rutherford, J. L.; Sitter, B.; Stewart, A.
M., III; Vetelino, M. G.; Wei, L., Org. Process Res. Dev. 2005, 9, 440.
60. Meyers, A. I.; Berney, D., Org. Synth. 1990, 69, 55.
92. Hutchison, J. M.; Hong, S.-p.; McIntosh, M. C., J. Org. Chem. 2004,
61. Boger, D. L.; Wolkenberg, S. E., J. Org. Chem. 2000, 65, 9120.
69, 4185.
62. Alimardanov, A. R.; Barrila, M. T.; Busch, F. R.; Carey, J. J.; Couturier,
M. A.; Cui, C., Org. Process Res. Dev. 2004, 8, 834. 93. De Jonghe, S.; Lamote, I.; Venkataraman, K.; Boldin, S. A.; Hillaert,
U.; Rozenski, J.; Hendrix, C.; Busson, R.; De Keukeleire, D.; Van
63. Cane, D. E.; Tan, W.; Ott, W. R., J. Am. Chem. Soc. 1993, 115, 527.
Calenbergh, S.; Futerman, A. H.; Herdewijn, P., J. Org. Chem. 2002,
64. Watson, T. J.; Ayers, T. A.; Shah, N.; Wenstrup, D.; Webster, M.; Freund, 67, 988.
D.; Horgan, S.; Carey, J. P., Org. Process Res. Dev. 2003, 7, 521.
94. Marshall, J. A.; Palovich, M. R., J. Org. Chem. 1998, 63, 3701.
65. Yamazaki, N.; Dokoshi, W.; Kibayashi, C., Org. Lett. 2001, 3, 193.
95. Meta, C. T.; Koide, K., Org. Lett. 2004, 6, 1785.
66. Yu, Q.-s.; Pei, X.-F.; Holloway, H. W.; Greig, N. H.; Brossi, A., J. Med.
96. Myers, A. G.; Goldberg, S. D., Tetrahedron Lett. 1998, 39, 9633.
Chem. 1997, 40, 2895.
97. Radinov, R.; Schnurman, E. S., Tetrahedron Lett. 1999, 40, 243.
67. Jeffery, J. E.; Kerrigan, F.; Miller, T. K.; Smith, G. J.; Tometzki, G. B.,
J. Chem. Soc., Perkin Trans. 1 1996, 2583. 98. Gu, Y.; Snider, B. B., Org. Lett. 2003, 5, 4385.
68. Zubarev, A. A.; Zav’yalova, V. K.; Litvinov, V. P., Russ. Chem. Bull. 99. Piers, E.; McEachern, E. J.; Romero, M. A., Tetrahedron Lett. 1996,
Int. Ed. 2004, 53, 626. 37, 1173.
69. Han, Z.; Krishnamurthy, D.; Pflum, D.; Grover, P.; Wald, S. A.; 100. Pearson, W. H.; Hines, J. V., J. Org. Chem. 2000, 65, 5785.
Senanayake, C. H., Org. Lett. 2002, 4, 4025. 101. Konno, T.; Ishihara, T.; Yamanaka, H., Tetrahedron Lett. 2000, 41,
70. Kawasaki, T.; Terashima, R.; Sakaguchi, K.-e.; Sekiguchi, H.; 8467.
Sakamoto, M., Tetrahedron Lett. 1996, 37, 7525. 102. Konno, T.; Chae, J.; Tanaka, T.; Ishihara, T.; Yamanaka, H., J. Fluorine
71. Yajima, A.; Mori, K., Tetrahedron Lett. 2000, 41, 351. Chem. 2006, 127, 36.
72. Harris, P. W. R.; Woodgate, P. D., Tetrahedron 2000, 56, 4001. 103. Cao, H.; van Ornum, S. G.; Deschamps, J.; Flippen-Anderson, J.; Laib,
73. Barluenga, J.; Fernández-Mari, F.; Viado, A. L.; Aguilar, E.; Olano, B., F.; Cook, J. M., J. Am. Chem. Soc. 2005, 127, 933.
J. Org. Chem. 1996, 61, 5659. 104. Crousse, B.; Alami, M.; Linstrumelle, G., Synlett 1997, 992.
74. Dondoni, A.; Fantin, G.; Fogagnolo, M.; Medici, A.; Pedrini, P., J. Org. 105. Potter, G. A.; Barrie, S. E.; Jarman, M.; Rowlands, M. G., J. Med. Chem.
Chem. 1989, 54, 702. 1995, 38, 2463.

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8 SODIUM BIS(2-METHOXYETHOXY)ALUMINUM HYDRIDE

106. Solà, L.; Castro, J.; Moyano, A.; Pericas, M. A.; Riera, A., Tetrahedron 127. Choshi, T.; Tonari, A.; Yoshioka, H.; Harada, K.; Sugino, E.; Hibino,
Lett. 1992, 33, 2863. S., J. Org. Chem. 1993, 58, 7952.
107. Weckerle, B.; Schreier, P.; Humpf, H.-U., J. Org. Chem. 2001, 66, 8160. 128. Ito, Y.; Miyake, T.; Hatano, S.; Shima, R.; Ohara, T.; Suginome, M., J.
108. Tanner, D.; He, H. M.; Somfai, P., Tetrahedron 1992, 48, 6069. Am. Chem. Soc. 1998, 120, 11880.
109. Dubuffet, T.; Bidon, C.; Sauvêtre; Raymond; Normant, J.-F., J. 129. Saitoh, T.; Jimbo, N.; Ichikawa, J., Chem. Lett. 2004, 33, 1032.
Organomet. Chem. 1990, 393, 173. 130. Hanaya, T.; Okamoto, R.; Prikhod’ko, Y. V.; Armour, M. A.; Hogg, A.
110. Chong, J. M.; Mar, E. K., J. Org. Chem. 1992, 57, 46. M.; Yamamoto, H., J. Chem. Soc., Perkin Trans. 1 1993, 1663.
111. Jones, D. W.; Thompson, A. M., J. Chem. Soc., Perkin Trans. 1 1993, 131. Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R.
2541. R., J. Am. Chem. Soc. 1998, 120, 4041.
112. Pasetto, P.; Franck, R. W., J. Org. Chem. 2003, 68, 8042. 132. Burck, S.; Gudat, D.; Nieger, M.; Du Mont, W.-W., J. Am. Chem. Soc.
113. Roos, G. H. P.; Donovan, A. R., Tetrahedron: Asymmetry 1999, 10, 991. 2006, 128, 3946.
114. Ayad, T.; Génisson, Y.; Verdu, A.; Baltas, M.; Gorrichon, L., 133. Guillen, F.; Rivard, M.; Toffano, M.; Legros, J.-Y; Daran, J.-C; Fiaud,
Tetrahedron Lett. 2003, 44, 579. J.-C., Tetrahedron 2002, 58, 5895.
115. Kakei, H.; Nemoto, T.; Ohshima, T.; Shibasaki, M., Angew. Chem. Int. 134. Percy, J. M.; Wilkes, R. D., Tetrahedron 1997, 53, 14749.
Ed. 2004, 43, 317. 135. Kim, B.-H; Woo, H.-G; Kim, W.-G; Yun, S.-S; Hwang, T.-S., Bull.
116. Tanner, D.; Groth, T., Tetrahedron 1997, 53, 16139. Korean Chem. Soc. 2000, 21, 211.
117. Orsini, F.; Pelizzoni, F., Tetrahedron: Asymmetry 1996, 7, 1033. 136. Wielstra, Y.; Meetsma, A.; Gambarotta, S., Organometallics 1989, 8,
258.
118. Dominguez, B. M.; Cullis, P. M., Tetrahedron Lett. 1999, 40, 5783.
137. Fujita, K.; Yorimitsu, H.; Oshima, K., Bull. Chem. Soc. Jpn. 2004, 77,
119. Hasegawa, K.; Arai, S.; Nishida, A., Tetrahedron 2006, 62, 1390.
1727.
120. Wong, C.-H; Provencher, L.; Porco, J. A.; Jung, S.-H; Wang, Y.-F;
138. Steed, J. W.; Tocher, D. A., J. Chem. Soc., Dalton Trans. 1993, 3187.
Chen, L.; Wang, R.; Steensma, D. H., J. Org. Chem. 1995, 60, 1492.
139. Takami, K.; Mikami, S.; Yorimitsu, H.; Shinokubo, H.; Oshima, K., J.
121. Tomàs, S.; Prohens, R.; Vega, M.; Rotger, M. C.; Deyà, P. M.; Ballester,
Org. Chem. 2003, 68, 6627.
P.; Costa, A., J. Org. Chem. 1996, 61, 9394.
140. Nemoto, T.; Ohshima, T.; Shibasaki, M., J. Am. Chem. Soc. 2001, 123,
122. Toure, B. B.; Hall, D. G., J. Org. Chem. 2004, 69, 8429.
9474.
123. Higashiyama, K.; Inoue, H.; Yamauchi, T.; Takahashi, H., J. Chem.
141. Esumi, T.; Fukuyama, H.; Oribe, R.; Kawazoe, K.; Iwabuchi, Y.; Irie,
Soc., Perkin Trans. 1 1995, 111.
H.; Hatakeyama, S., Tetrahedron Lett. 1997, 38, 4823.
124. Miyata, O.; Koizumi, T.; Asai, H.; Iba, R.; Naito, T., Tetrahedron 2004,
142. Tilstam, U.; Weinmann, H., Org. Process Res. Dev. 2002, 6, 906.
60, 3893.
143. Woo, H.-G.; Song, S.-J.; Kim, B.-H., Bull. Korean Chem. Soc. 1998,
125. Grundt, P.; Williams, I. A.; Lewis, J. W.; Husbands, S. M., J. Med.
19, 1161.
Chem. 2004, 47, 5069.
144. Woo, H.-G.; Kim, S.-Y.; Han, M.-K.; Cho, E. J.; Jung, I. N.,
126. Fresneda, P. M.; Molina, P.; Delgado, S., Tetrahedron 2001, 57, 6197.
Organometallics 1995, 14, 2415.

A list of General Abbreviations appears on the front Endpapers