Diastereoselective allylation and crotylation reactions of aldehydes with potassium allyl- and crotyltrifluoroborates under Lewis acid catalysis

Article abstract of DOI:10.1055/s-2000-6303

Potassium allyl- and crotyltrifluoroborates react with aldehydes in a process catalyzed by a variety of Lewis acids, to give the corresponding homoallylic alcohols. Of the Lewis acids examined, BF₃·OEt₂, used either stoichiometrically or catalytically, was found to most efficiently catalyze this reaction. The air and moisture stable potassium organotrifluoroborate salts react with a variety of alkyl, α- or β- substituted alkyl, and aryl aldehydes, and lead to the adducts in high yield and with high diastereoselectivity.

Full text of DOI:10.1055/s-2000-6303

990
PAPER
Diastereoselective Allylation and Crotylation Reactions of Aldehydes with
Potassium Allyl- and Crotyltrifluoroborates under Lewis Acid Catalysis
Robert A. Batey,* Avinash N. Thadani, David V. Smil, Alan J. Lough†
Department of Chemistry, Lash Miller Laboratories, 80 St. George Street, University of Toronto, Toronto, Ontario, M5S 3H6, Canada
Fax +1(416)9785059; E-mail: rbatey@chem.utoronto.ca
Received 16 February 2000
co-workers recently showed potassium aryltrifluorobo-
Abstract: Potassium allyl- and crotyltrifluoroborates react with al-
rates (ArBF3K) to be useful precursors for the formation
dehydes in a process catalyzed by a variety of Lewis acids, to give
of arylboron difluoride Lewis acids,7a and reported their
preparation using aqueous KHF2. Similarly, we reasoned
found to most efficiently catalyze this reaction. The air and moisture that potassium allyl- and crotyltrifluoroborate 3 should be
the corresponding homoallylic alcohols. Of the Lewis acids exam-
ined, BF3◊OEt2, used either stoichiometrically or catalytically, was
stable potassium organotrifluoroborate salts react with a variety of
alkyl, a- or b- substituted alkyl, and aryl aldehydes, and lead to the
convenient precursors for the in situ formation of allylbo-
ron difluoride, a species theoretically predicted to have
adducts in high yield and with high diastereoselectivity.
higher reactivity in allylation processes.9
Key words: allylations, boron, alcohols, Lewis acids, catalysis
The preparation of the potassium allyl- and crotyltrifluo-
roborates 3 was achieved via the boronic acids in a man-
ner analogous to that used for the synthesis of other
potassium trifluoroborate salts (Scheme 2). The addition
Synthetically versatile homoallylic alcohols 2 are typical-
of either allylmagnesium bromide10 or crotylpotassium11
to trimethylborate or triisopropylborate respectively, fol-
lowed by acidic hydrolysis, was used to prepare the requi-
site allyl- and crotylboronic acids, respectively.
Conversion to the potassium allyl- or crotyltrifluoroborate
3was then achieved by treatment with aqueous KHF2, fol-
lowed by recrystallization from acetonitrile. Particular
care should be taken to avoid isomerization of (E)-croty-
lpotassium during the preparation of 3c.11 The salts 3 are
air and water stable solids, and can be stored for extended
periods of time at room temperature, in plastic bottles with
no further precautions.
ly prepared by the allylation and crotylation of alde-
hydes.1,2 A variety of organometallic reagents have been
used for these transformations, but allyl- and crotylboron
compounds 1 are particularly useful because of the high
yields and excellent levels of stereo control they provide
(Scheme 1).3 Of the two main classes of 1, allyl/crotyl di-
alkylboranes 1a and allyl/crotyl boronates 1b, only one
reagent, allyl pinacol boronate, is commercially available
at the present time.4 A degree of inconvenience is often as-
sociated with other allyl- and crotylboron compounds,
which are usually prepared immediately prior to use due
to their sensitivity to air and/or moisture, and the difficul-
ties involved with their subsequent storage and handling.
As part of our ongoing research in organoboron chemis-
try,5 we recently reported a new class of allyl- and crotyl-
(i) B(OMe)3, THF, -78 °C
MgBr
K
BF3
boron
compounds,
potassium
allyl-
and
(ii) HCl, H2O, 0 °C
(iii) KHF2, H2O, r.t.
3a, 76 %
crotyltrifluoroborates, and their BF3∑OEt2 catalyzed addi-
tion to carbonyl compounds.6 We now report the use of
other Lewis acid catalysts, and the reaction of potassium
allyltrifluoroborate with aldehydes bearing a- or b-stereo-
centres.
R1
R1
(i) nBuLi, KOtBu, THF, -78 °C
R2
R2
BF3
(ii) B(OiPr)3, -78 °C
(iii) HCl, H2O, 0 °C
(iv) KHF2, H2O, r.t.
K
3b R1 = Me, R2 = H, 70 %
3c R1 = H, R2 = Me, 71 %
R1
Scheme 2
OH
R1 = H, R2 = H
R1 = Me, R2 = H
R1 = H, R2 = Me
R3CHO
R3
R2
BX2
BR2
2
1
R1
R2
A variety of Lewis acids were screened to evaluate their
effectiveness at catalyzing the addition of allyltrifluoro-
borate 3a to 4-nitrobenzaldehyde (Table 1). By conduct-
ing the allylation at -78 °C in dichloromethane, it was de-
termined that with 2 equivalents of BF3∑OEt2, full
conversion was achieved within 15 minutes, and the iso-
lated product yield of 4a was 93%. Other Lewis acids also
promoted the reactions, but showed lower degrees of con-
version under the same reaction conditions. Reaction of
the salts does not occur in the absence of a Lewis acid cat-
alyst even at elevated temperatures, presumably due to the
R1
R1
R1
R2
R2
R2
K
BF3
B(OR)2
1a
1b
3
Scheme 1
Organotrifluoroborate salts (RBF3M, M = alkali metal)5a,7
have been demonstrated to be more air and water stable
than the corresponding boronic acids.8 Vedejs and
Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Diastereoselective Allylation and Crotylation Reactions of Aldehydes
991
Table 1 Effect of Lewis acids on the Allylation of 4-Nitrobenzalde-
hyde with Allyltrifluoroborate 3a
While requiring significantly longer reaction times, the
use of catalytic BF3∑OEt2 gave comparable yields of 4.
O
OH
Crotylation using (Z)- and (E)-potassium crotyltrifluoro-
borate 3b/c was found to work equally well using either
methods A or B, leading to products 5 with excellent lev-
els of stereocontrol and in uniformly high yields (Table 3).
The (Z)-crotyltrifluoroborate 3b consistently gave rise to
the syn-diastereomer, while the (E)-crotyltrifluoroborate
3c gave the expected anti-product. Each of these observa-
tions is consistent with addition of a tri-coordinate boron
species via a Zimmerman-Traxler like transition state.
The identity of the active allylation species has not been
established, but allylboron difluoride, is presumably ini-
tially formed in situ under these conditions, by the Lewis
acid promoted removal of fluoride from the salts 3.
H
Lewis Acid
K+
+
BF3
3a
CH2Cl2, -78 °C
O2N
O2N
4a
15 min
Entry
Lewis Acid
B(OMe)3
AlCl3
Conversion [%]
Yield [%]
1
2
3
4
5
6
<5
20
–
16
20
28
41
93
Ti(OiPr)4
TMSCl
25
35
SnCl4
50
The reaction of allyl and crotyl metal reagents with alde-
hydes containing adjacent stereocenters is of importance
in the context of acyclic stereoselective synthesis.12 The
general method employing catalytic BF3∑OEt2 (Method
B) can be applied to the allylation of aldehydes with an a-
or b-stereocenter. We chose to examine aldehydes 6 and 8
containing either an a- or b-tert-butyldimethylsilanyloxy
substituent, respectively. Unfortunately, allylation of 6
and 8 with 3a gave only modest diastereoselection,
though the overall yields were generally high (Table 4, en-
tries 1, 2 and Table 5, entries 1, 2). Prior studies by Hoff-
mann and co-workers in the reaction of a similar a-
benzyloxy substituted aldehyde with allyl pinacol bor-
onate also displayed only modest diastereoselectivity.12a
In contrast, the crotylation of 6 with 3b/c displayed great-
er levels of diastereoselectivity (Table 4, entries 3-6).
The (Z)-crotyl reagent 3b shows very good anti selectivity
while the corresponding (E)-crotyl reagent 3c displays
more modest syn selectivity in the reaction with 2-(tert-
butyldimethylsilanyloxy)propanal (Table 4, entries 3, 4).
These results are consistent with prior studies by both
Hoffmann12b and Roush12c on crotylboration of similar a-
alkoxy substituted aldehydes, and have been rationalized
by invoking Cornforth-like transition states.3a, 12b,c, 13 In
contrast, the reactions of both 3b and 3c with 2--(tert-bu-
tyldimethylsilanyloxy)-2-phenylacetaldehyde (Table 4,
Entries 5,6) displayed good anti selectivity. Roush has
proposed transition states to account for this type of seem-
ingly anomolous behaviour in the context of enoloate ad-
ditions to aldehydes.13c
BF3◊Et2O
100
insolubility of 3 in dichloromethane. This feature distin-
guishes the reactivity of 3 from most allylboron com-
pounds, which do not require prior activation.
Having established BF3∑OEt2 as the most efficient pro-
moter for the allylation process, a variety of substituted
and unsubstituted aryl and alkyl aldehydes were then
allylated to give the homoallylic alcohols 4 in high isolat-
ed yields (Table 2). Two protocols were employed, using
either 2 equivalents of BF3∑OEt2 with two equivalents of
3a at -78 °C in dichloromethane over 15 minutes (Meth-
od A), or with 5 mol% of BF3∑OEt2 with 2 equivalents of
3a at room temperature over 3-6 hours (Method B).
Table 2 Allylation of Aldehydes with Allyltrifluoroborate 3a
OH
O
BF3·OEt2
+
K+
R1
R1
H
Method A or B
BF3
3a
4
Entry R1
Product Yield [%]
Yield [%]
(Method Aa) (Method Bb)
1
2
3
4
5
6
7
8
9
4-O2NC6H4
4a
4b
4c
4d
4e
4f
96
82
89
93
95
90
95
85
84
95
84
91
91
89
93
95
86
85
n-C7H15
(E)-Ph-CH=CH-
Ph
Both allylation and crotylation of 8 (Table 5), on the other
hand, only displayed modest diastereoselectivity presum-
ably due to the fact that the b-stereocenter is remote from
the site of the newly developing C-C bond. Roush and co-
workers previously reported that the reaction of allyl pina-
col boronate with a b-alkoxy substituted aldehyde also
proceeded with modest diastereoselectivity.12d
4-MeOC6H4
4-MeSC6H4
4-NCC6H4
3,4-Cl2C6H3
4g
4h
In conclusion, we have demonstrated the viability of po-
tassium allyl- and crotyltrifluoroborates as air and mois-
ture stable reagents for allylation and crotylation of
aldehydes. These reagents offer several advantages over
existing allylboron reagents, including rapid and high
3-MeO-4-HOC6H3 4i
a BF3◊Et2O (2.0 equiv.), 3a (2.0 equiv.), CH2Cl2, –78°C, 15 mins.
b BF3◊Et2O (0.05 equiv.), 3a (2.0 equiv.), CH2Cl2, rt, 3–6 h.
Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York

992
R. A. Batey et al.
PAPER
Table 3 Crotylation of Aldehydes With (Z)- and (E)-Crotyltrifluoroborates 3b/c
OH
R1
O
BF3·OEt2
R3
+
R3
H
BF3
R2
Method A or B
K
5
R1 R2
3b/c
Entry
R1
R2
R3
Product
d.r.
Yield [%]
Yield [%]
(Method Aa)
(Method Bb)
1
2
3
4
5
6
7
8
Me
H
H
n-C7H15
n-C7H15
Ph
5a
5b
5c
5d
5e
5f
> 98 : 2
> 98 : 2
> 98 : 2
> 98 : 2
96 : 4
74
84
91
94
91
91
95
96
76
85
92
93
93
95
94
94
Me
H
Me
H
Me
H
Ph
Me
H
4-MeOC6H4
4-MeOC6H4
4-O2NC6H4
4-O2NC6H4
Me
H
97 : 3
Me
H
5g
5h
> 98 : 2
> 98 : 2
Me
a BF3◊Et2O (2.0 equiv.), 3b/c (2.0 equiv.), CH2Cl2, –78°C, 15 mins.
b BF3◊Et2O (0.05 equiv.), 3b/c (2.0 equiv.), CH2Cl2, r.t., 3–6 h.
yielding additions, and excellent levels of diastereocon-
trol. We are currently working on extending the scope of
these useful reagents and developing milder protocols for
their additions.
were recorded on a Perkin-Elmer Spectrum 1000, with samples
loaded as neat films on NaCl plates or as KBr discs. Low resolution
mass spectra were recorded on a Bell and Howell 21-490 spectro-
meter, and high resolution spectra were recorded on an AEI
MS3074 spectrometer. Silica gel (60 Å, 230-400 mesh) was ob-
tained from Whatman Company or Toronto Research Chemicals,
Inc. Elemental analysis were obtained from Canadian Microanaly-
tical Service Ltd., Delta, BC.
Reagents were used as received. THF was distilled from Na metal/
benzophenone ketyl under Ar. CH2Cl2 was distilled from CaH2. All
other solvents used were reagent grade. All manipulations were car-
ried out under N2 atm. Proton chemical shifts were internally refer-
enced to the residual proton resonance in CDCl3 (d = 7.26 ppm) or
CD3CN (d = 1.94 ppm). Carbon chemical shifts were internally ref-
erenced to the deuterated solvent signals in CDCl3 (d = 77.00 ppm)
or CD3CN (d = 1.32 ppm). Boron chemical shifts were externally
referenced to BF3∑OEt2 (d = 0.00 ppm). Fluorine chemical shifts
were externally referenced to CFCl3 (d = 0.00 ppm). FT-IR spectra
Potassium Allyltrifluoroborate (3a)
To a solution of trimethylborate (22.7 mL, 0.200 mol) in Et2O (300
mL) cooled to -78 °C was added allylmagnesium bromide (1.0 M
in Et2O, 200 mL, 0.200 mol) slowly over approx. 30 min. The reac-
tion mixture was stirred for 2 h at -78 °C and then poured immedi-
Table 4 Allylation and Crotylation of Aldehydes 6 with 3
O
OH
OH
R1
R3
R3
R3
5 mol % BF3·OEt2
+
+
H
R2
CH2Cl2, rt, 6h
K
BF3
R1
syn
R1
anti
TBSO
R2
TBSO
R2
OTBS
6
3
7
Entry
R1
H
R2
R3
Product
7a
syn : anti
30 : 70
35 : 65
5 : 95a
Yield [%]
1
2
3
4
5
6
H
Me
Ph
69
91
73
72
85
82
H
H
7b
Me
H
H
Me
Me
Ph
7c
Me
H
7d
75 : 25
10 : 90b
10 : 90c
Me
H
7e
Me
Ph
7f
a Trace amounts of 7d-syn also present in isolated adducts.
b Trace amounts of 7f-syn also present in isolated adducts. The stereochemistry of the major diastereomer was confirmed by single crystal
X-ray analysis. The authors have deposited the atomic coordinates of this compound at the Cambridge Crytallographic Data Centre.
c The stereochemistry was confirmed by derivatization through deprotection (TBAF) and acetalization with 2,2-dimethoxypropane.
The benzylic proton of the resultant ketal appears as a doublet (J = 8.7 Hz) consistent with cis-orientation of the hydrogen atoms.
Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Diastereoselective Allylation and Crotylation Reactions of Aldehydes
993
Table 5 Allylation and Crotylation of Aldehydes 8 with 3
R1
TBSO
R3
OH
TBSO
R3
OH
TBSO
R3
O
5 mol % BF3·OEt2
+
+
H
R2
K
BF3
CH2Cl2, r.t., 6h
R1 R2
R1 R2
syn
anti
8
3
9
Entry
R1
R2
R3
iPr
Ph
Ph
Ph
Product
9a
syn : anti
35 : 65
Yield [%]
1
2
3
4
H
H
90
86
84
87
H
H
9b
30 : 70
Me
H
9c
25 : 75a
25 : 75a
H
Me
9d
a The stereochemistry of these compounds were confirmed via conversion to the corresponding acetonide ((i) TBAF, (ii) 2,2-dimethoxy-
propane) and assigned according to Rychnovsky’s protocol.14
ately into an Erlenmeyer flask containing 2 N HCl (300 mL). The
resulting biphasic solution was vigorously stirred for 30 min. The
layers were separated and the aqueous layer extracted with Et2O
(3 ¥ 75 mL). The combined organic extracts were concentrated in
vacuo to afford a pale yellow oil. KHF2 (3.5 M in H2O, 156 mL,
0.700 mol) was then added, the reaction mixture stirred for 30 min
at r.t. and subsequently stored at 4 °C for 12 h. The white precipitate
was filtered off and recrystallized from CH3CN to afford 3a as a
white solid (22.5 g, 76%).
19F NMR (CD3CN, 376 MHz): d = -140.1 (q, J = 58.6 Hz).
MS (FAB): m/z = 287 (23), 286 (16), 285 (37), 269 (24), 125 (28),
124 (13), 123 (100), 122 (29).
HRMS (FAB): m/z calcd for (C4H7BF3)- 123.0592. Found:
123.0587.
Anal. Calcd for C4H7BF3K: C, 29.66; H, 4.36. Found: C, 29.23; H,
4.61.
1H NMR (CD3CN, 500 MHz): d = 6.00-5.89 (m, 1H), 4.75 (d, 1H,
J = 17.0 Hz), 4.66 (d, 1H, J = 10.0 Hz), 1.12 (br s, 2H).
13C NMR (CD3CN, 125 MHz): d = 142.82, 111.12, 27.20 (br).
11B NMR (CD3CN, 160 MHz): d = 4.98 (q, J = 58.6 Hz).
19F NMR (CD3CN, 376 MHz): d = -140.1 (q, J = 58.6 Hz).
MS (FAB): m/z = 257 (53), 256 (27), 109 (100).
(E)-Potassium Crotyltrifluoroborate (3c)
To a solution of trans-2-butene (23.0 mL, 0.225 mol) in THF (150
mL) at -78 °C was added potassium tert-butoxide (22.4 g, 0.200
mol). n-BuLi (2.5 M in hexanes, 80.0 mL, 0.200 mol) was then add-
ed at a rate such that the internal temperature did not exceed -60 °C.
After the addition was complete, the internal temperature of the re-
action mixture was allowed to rise to -50 °C. The reaction mixture
was stirred for 15 min at this temperature prior to being recooled to
-78 °C. Triisopropylborate was then added at a rate such that the in-
ternal temperature did not rise above -60 °C. The rest of the proce-
dure is exactly the same as that for 3b. The title compound was
isolated as a white solid (23.0 g, 71%).
HRMS (FAB): m/z calcd for (C3H5BF3)- 109.0436. Found:
109.0436.
Anal. Calcd for C3H5BF3K: C, 24.35; H, 3.41. Found: C, 24.26; H,
3.42.
1H NMR (CD3CN, 500 MHz): d = 5.56-5.44 (m, 1H), 5.16-5.04
(m, 1H), 1.56 (dq, 3H, J = 6.5, 1.5 Hz), 0.97 (br s, 2H).
(Z)-Potassium Crotyltrifluoroborate (3b)
13C NMR (CD3CN, 125 MHz): d = 133.67, 120.16, 19.8 (br), 12.88.
11B NMR (CD3CN, 160 MHz): d = 4.98 (q, J = 58.6 Hz).
19F NMR (CD3CN, 376 MHz): d = -140.1 (q, J = 58.6 Hz).
To a solution of cis-2-butene (23.0 mL, 0.225 mol) in THF (150
mL) at -78 °C was added potassium tert-butoxide (22.4 g, 0.200
mol). n-BuLi (2.5 M in hexanes, 80.0 mL, 0.200 mol) was then add-
ed at a rate such that the internal temperature did not exceed -50 °C.
After the addition was complete, the internal temperature of the re-
action mixture was allowed to rise to -20 °C to -25 °C for 45 min
prior to being recooled to -78 °C. Triisopropylborate was then
added at a rate such that the internal temperature did not rise above
-50 °C. The reaction mixture was subsequently stirred for an addi-
tional 45 min and then rapidly poured into a separatory funnel con-
taining 1 N HCl (400 mL) saturated with NaCl. The layers were
separated and the aqueous layer extracted with Et2O (4 × 100 mL).
The combined organic extracts were concentrated in vacuo to afford
a clear, colorless oil, which was redissolved in MeOH (25 mL).
KHF2 (3.5 M in H2O, 156 mL, 0.700 mol) was then added, the re-
action mixture stirred for 30 min at r.t., and subsequently stored at
4 °C for 12 h. The white precipitate was filtered off and recrystal-
lized from CH3CN to afford 3b as a white solid (22.7 g, 70%).
MS (FAB): m/z = 287 (13), 286 (11), 285 (52), 284 (29), 283 (14),
123 (100), 122 (30).
HRMS (FAB): m/z calcd for (C4H7BF3)- 123.0592. Found:
123.0576.
Allylation/Crotylation Reaction; Typical Procedure
Method A
To a suspension of the aldehyde (1.00 mmol) and potassium allyl-
trifluoroborate (296 mg, 2.00 mmol) in CH2Cl2 (10 mL) at -78 °C
was added BF3◊OEt2 (0.25 mL, 1.97 mmol). The reaction mixture
was stirred for 15 min at -78 °C and then quenched with sat.
NaHCO3 (10 mL). The reaction mixture was then allowed to warm
to r.t. The layers were separated and the aqueous layer extracted
with CH2Cl2 (3 ¥ 10 mL). The combined organic extracts were
dried (MgSO4), filtered and concentrated in vacuo to afford a clear,
colourless oil. The homoallylic alcohol was purified by flash chro-
matography (silica gel), EtOAc/hexanes (2:8), to afford the com-
pounds as clear, colourless oils.
1H NMR (CD3CN, 300 MHz): d = 5.62-5.49 (m, 1H), 5.23-5.11
(m, 1H), 1.56 (dd, 3H, J = 6.5, 1.0 Hz), 1.01 (br s, 2H).
13C NMR (CD3CN, 125 MHz): d = 133.67, 120.16, 19.5 (br), 12.88.
11B NMR (CD3CN, 160 MHz): d = 4.98 (q, J = 58.6 Hz).
Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York

994
R. A. Batey et al.
PAPER
Method B
4-(1-Hydroxybut-3-enyl)benzonitrile (4g)15e
To a suspension of the aldehyde (1.00 mmol) and potassium allyl-
trifluoroborate (296 mg, 2.00 mmol) in CH2Cl2 (10 mL) at r.t. was
added BF3∑OEt2 (60 mL, 0.05 mmol). The reaction mixture was
stirred for 3-6 h. The rest of the procedure is the same as per Meth-
od A.
1H NMR (CDCl3, 400 MHz): d = 7.58 (d, 2H, J = 8.5 Hz), 7.43 (d,
2H, J = 8.0 Hz), 5.79-5.68 (m, 1H), 5.14-5.08 (m, 2H), 4.76 (dd,
1H, J = 7.5, 5.0 Hz), 2.73 (br s, 1H), 2.52-2.36 (m, 2H).
13C NMR (CDCl3, 100 MHz): d = 149.22, 133.27, 132, 126.39,
119.01, 118.72, 110.72, 72.24, 43.57.
1-(4-Nitrophenyl)but-3-en-1-ol (4a)
4-(3,4-Dichlorophenyl)but-3-en-1-ol (4h)15f
IR (NaCl, thin film): n = 3418, 3120, 2980, 2910, 1665, 1605, 1520,
1H NMR (CDCl3, 400 MHz): d = 7.42 (d, 1H, J = 2.0 Hz), 7.38 (d,
1H, J = 8.0 Hz), 7.13 (dd, 1H, J = 8.0, 2.0 Hz), 5.79-5.67 (m, 1H),
5.16-5.10 (m, 2H), 4.64 (dd, 1H, J = 7.5, 5.0 Hz), 2.57 (br s, 1H),
2.50-2.34 (m, 2H).
1348, 1058, 922, 855, 754, 700 cm-1
1H NMR (CDCl3, 400 MHz): d = 8.17 (d, 2H, J = 8.5 Hz), 7.51 (d,
2H, J = 8.5 Hz), 5.83-5.71 (m, 1H), 5.20-5.12 (m, 2H), 4.88-4.82
(m, 1H), 2.58-2.50 (m, 1H), 2.48-2.39 (m, 2H).
13C NMR (CDCl3, 100 MHz): d = 151.11, 147.11, 133.15, 126.50,
123.54, 119.50, 72.11, 43.80.
MS (EI): m/z = 194 (M+, 6), 153 (16), 152 (100), 122 (13), 106 (21),
105 (16), 94 (16), 78 (19), 77 (19).
13C NMR (CDCl3, 100 MHz): d = 143.94, 133.41, 132.30, 131.10,
130.20, 127.73, 125.09, 119.09, 71.87, 43.61.
4-(1-Hydroxybut-3-enyl)-2-methoxyphenol (4i)15g
IR (NaCl, thin film): n = 3422, 2936, 1640, 1604, 1517, 1465, 1431,
1374, 1270, 1235, 1153, 1124, 1034, 916, 858, 820 cm-1.
HRMS (EI): m/z calcd for C10H12NO3 194.0817. Found: 194.0816.
1H NMR (CDCl3, 400 MHz): d = 6.87 (d, 1H, J = 2.0 Hz), 6.83 (d,
1H, J = 8.0 Hz), 6.77 (dd, 1H, J = 8.0, 2.0 Hz), 5.83-5.71 (m, 2H),
5.15-5.07 (m, 2H), 4.61 (t, 1H, J = 6.5 Hz), 3.83 (s, 3H), 2.46 (t,
2H, J = 7.0 Hz), 2.33 (br s, 1H).
13C NMR (CDCl3, 100 MHz): d = 146.53, 144.90, 135.89, 134.57,
118.74, 118.07, 114.10, 108.32, 73.23, 55.77, 43.66.
Undec-1-en-4-ol (4b)15a
1H NMR (CDCl3, 400 MHz): d = 5.88-5.75 (m, 1H), 5.15-5.08 (m,
2H), 3.65-3.57 (m, 1H), 2.32-2.24 (m, 1H), 2.15-2.07 (m, 1H),
1.60 (br s, 1H), 1.48-1.18 (m, 12H), 0.86 (t, 3H, J = 7.0 Hz).
13C NMR (CDCl3, 100 MHz): d = 134.91, 118.03, 70.66, 41.92,
36.80, 31.80, 29.60, 29.26, 25.66, 22.64, 14.08.
MS (EI): m/z = 194 (M+, 4), 154 (14), 153 (100), 151 (8), 125 (30),
123 (5), 110 (12), 94 (8), 93 (72), 65 (38).
HRMS (CI-): m/z calcd for C11H13O3 (M-H)- 193.0865. Found:
193.0853.
1-Phenylhexa-1,5-dien-3-ol (4c)15b
1H NMR (CDCl3, 400 MHz): d = 7.41-7.36 (m, 2H), 7.31 (t, 2H,
J = 7.5 Hz), 7.27-7.21 (m, 1H), 6.60 (d, 1H, J = 16.0 Hz), 6.24 (dd,
1H, J = 16.0, 6.5 Hz), 5.93-5.80 (m, 1H), 5.23-5.16 (m, 2H), 4.35
(q, 1H, J = 6.5 Hz), 2.48-2.34 (m, 2H), 2.03 (s, 1H).
(3R*,4R*)-3-Methylundec-1-en-4-ol (5a)16a
1H NMR (CDCl3, 400 MHz): d = 5.83-5.73 (m, 1H), 5.12-5.03 (m,
2H), 3.50-3.44 (m, 1H), 2.31-2.21 (m, 1H), 1.51 (br s, 1H), 1.50-
1.44 (m, 2H), 1.39-1.22 (m, 10H), 1.01 (d, 3H, J = 7.0 Hz), 0.87 (t,
3H, J = 6.5 Hz).
13C NMR (CDCl3, 100 MHz): d = 136.57, 133.98, 131.49, 130.24,
128.49, 127.57, 126.41, 118.38, 71.64, 41.92.
1-Phenylbut-3-en-1-ol (4d)15c
13C NMR (CDCl3, 100 MHz): d = 141.10, 115.11, 74.65, 43.36,
33.96, 31.81, 29.63, 29.28, 26.07, 22.63, 14.07, 13.95.
1H NMR (CDCl3, 400 MHz): d = 7.42-7.25 (m, 5H), 5.90-5.75 (m,
1H), 5.17 (d, 1H, J = 18.0 Hz), 5.15 (d, 1H, J = 10.0 Hz), 4.73 (t,
1H, J = 6.5 Hz), 2.58-2.45 (m, 2H), 2.29 (br s, 1H).
(3S*,4R*)-3-Methylundec-1-en-4-ol (5b)16b
13C NMR (CDCl3, 100 MHz): d = 143.80, 134.39, 128.31, 127.44,
125.74, 118.26, 73.23, 43.72.
1H NMR (CDCl3, 400 MHz): d = 5.74 (ddd, 1H, J = 16.5, 12.0, 8.0
Hz), 5.12-5.08 (m, 2H), 3.41-3.34 (m, 1H), 2.19 (hextet, 1H,
J = 7.0 Hz), 1.63 (br s, 1H), 1.53-1.43 (m, 2H), 1.40-1.22 (m,
10H), 1.02 (d, 3H, J = 7.0 Hz), 0.87 (t, 3H, J = 7.0 Hz).
1-(4-Methoxyphenyl)but-3-en-1-ol (4e)15d
1H NMR (CDCl3, 400 MHz): d = 7.27 (d, 2H, J = 8.5 Hz), 6.87 (d,
2H, J = 9.0 Hz), 5.82-5.73 (m, 1H), 5.18-5.09 (m, 2H), 4.67 (t, 1H,
J = 6.5 Hz), 3.79 (s, 3H), 2.48 (t, 2H, J = 7.0 Hz), 2.04 (br s, 1H).
13C NMR (CDCl3, 100 MHz): d = 140.34, 116.14, 74.65, 44.07,
34.20, 31.82, 29.67, 29.28, 25.72, 22.63, 16.25, 14.07.
13C NMR (CDCl3, 100 MHz): d = 158.96, 136.00, 134.58, 127.04,
(1S*,2R*)-2-Methyl-1-phenylbut-3-en-1-ol (5c)16c
118.21, 113.74, 72.93, 55.24, 43.73.
1H NMR (CDCl3, 400 MHz): d = 7.37-7.26 (m, 5H), 5.81-5.71 (m,
1H), 5.07-5.00 (m, 2H), 4.58 (dd, 1H, J = 5.5, 3.0 Hz), 2.63-2.53
(m, 1H), 2.20 (d, 1H, J = 3.0 Hz), 1.01 (d, 3H, J = 7.0 Hz).
1-(4-Methylsulfanylphenyl)but-3-en-1-ol (4f)
IR (NaCl, thin film): n = 3390, 3080, 2985, 2905, 1660, 1599, 1495,
1435, 1048, 915, 820 cm-1.
13C NMR (CDCl3, 100 MHz): d = 142.50, 140.21, 127.95, 127.23,
126.45, 115.40, 77.19, 44.54, 14.03.
1H NMR (CDCl3, 400 MHz): d = 7.26-7.18 (m, 4H), 5.81-5.70 (m,
1H), 5.16-5.08 (m, 2H), 4.64 (t, 1H, J = 6.5 Hz), 2.48-2.42 (m,
5H), 2.35 (br s, 1H).
13C NMR (CDCl3, 100 MHz): d = 140.70, 137.29, 134.22, 126.47,
126.28, 118.26, 72.78, 43.57, 15.78.
MS (EI): m/z = 194 (M+, 14), 154 (15), 153 (100), 110 (20), 109
(40), 79 (19), 78 (30), 77 (45).
(1S*,2S*)-2-Methyl-1-phenylbut-3-en-1-ol (5d)16c
1H NMR (CDCl3, 400 MHz): d = 7.37-7.24 (m, 5H), 5.81 (ddd, 1H,
J = 17.0, 10.5, 8.0 Hz), 5.23-5.16 (m, 2H), 4.34 (d, 1H, J = 8.0 Hz),
2.48 (sextet, 1H, J = 7.0 Hz), 2.29 (br s, 1H), 0.87 (d, 3H, J = 7.0
Hz).
13C NMR (CDCl3, 100 MHz): d = 142.36, 140.57, 128.14, 127.54,
126.78, 116.69, 77.74, 46.18, 16.43.
HRMS (EI): m/z calcd for C11H14OS 194.0765. Found: 194.0775.
Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Diastereoselective Allylation and Crotylation Reactions of Aldehydes
995
(1S*,2R*)-1-(4-Methoxyphenyl)-2-methylbut-3-en-1-ol (5e)16d
1H NMR (CDCl3, 400 MHz): d = 7.21 (d, 2H, J = 8.5 Hz), 6.86 (d,
2H, J = 9.0 Hz), 5.79-5.66 (m, 1H), 5.07-5.03 (m, 1H), 5.02-4.98
(m, 1H), 4.52 (d, 1H, J = 6.0 Hz), 3.79 (s, 3H), 2.61-2.48 (m, 1H),
2.14 (br s,1H), 1.02 (d, 3H, J = 7.0 Hz).
HRMS (CI-): m/z calcd for C12H25O2Si (M-H)- 229.1624. Found:
229.1613.
IR (NaCl, thin film): n = 3460, 3077, 2955, 2930, 2873, 2858, 1642,
1472, 1463, 1387, 1257, 1080, 1005, 968, 912, 836, 776, 668 cm-1.
13C NMR (CDCl3, 100 MHz): d = 158.78, 140.28, 134.73, 127.6,
(1S*,2S*)-1-(tert-Butyldimethylsilanyloxy)-1-phenylpent-4-en-
2-ol (7b-"syn")17b
115.35, 113.36, 76.98, 55.18, 44.62, 14.39.
1H NMR (CDCl3, 400 MHz): d = 7.35-7.25 (m, 5H), 5.90-5.79 (m,
1H), 5.08-5.01 (m, 2H), 4.45 (d, 1H, J = 7.0 Hz), 3.70-3.63 (m,
1H), 2.79 (d, 1H, J = 3.0 Hz), 2.18-2.10 (m, 1H), 2.09-2.00 (m,
1H), 0.90 (s, 9H), 0.05 (s, 3H), -0.21 (s, 3H).
(1S*,2S*)-1-(4-Methoxyphenyl)-2-methylbut-3-en-1-ol (5f)15d
1H NMR (CDCl3, 400 MHz): d = 7.25 (d, 2H, J = 9.0 Hz), 6.88 (d,
2H, J = 9.0 Hz), 5.81 (ddd, 1H, J = 17.0, 10.5, 8.0 Hz), 5.24-5.15
(m, 2H), 4.29 (d, 1H, J = 8.0 Hz), 3.80 (s, 3H), 2.45 (sextet, 1H,
J = 7.0 Hz), 2.29 (br s, 1H), 0.83 (d, 3H, J = 7.0 Hz).
13C NMR (CDCl3, 100 MHz): d = 159.04, 140.89, 134.58, 127.92,
116.53, 113.57, 77.43, 55.18, 46.28, 16.50.
13C NMR (CDCl3, 100 MHz): d = 141.31, 134.86, 128.13, 127.80,
127.07, 116.92, 78.49, 75.66, 36.63, 25.75, 18.08, -4.53, -5.13.
(1R*,2S*)-1-(tert-Butyldimethylsilanyloxy)-1-phenylpent-4-en-
2-ol (7b-"anti")17b
(1S*,2R*)-2-Methyl-1-(4-Nitrophenyl)but-3-en-1-ol (5g)
IR (NaCl, thin film): n = 3420, 3120, 2988, 2910, 1665, 1608, 1521,
1349, 1060, 922, 855, 754, 700 cm-1.
IR (NaCl, thin film): n = 3575, 3462, 3076, 3030, 2960, 2929, 2872,
2857, 1641, 1493, 1471, 1454, 1389, 1361, 1253, 1196, 1064, 1005,
913, 836, 778, 701, 674, 633 cm-1.
1H NMR (CDCl3, 400 MHz): d = 8.13 (d, 2H, J = 9.0 Hz), 7.45 (d,
2H, J = 8.5 Hz), 5.74 (ddd, 1H, J = 17.0, 10.5, 7.0 Hz), 5.07 (dt, 1H,
J = 10.5, 1.5 Hz), 5.03 (dt, 1H, J = 17.0, 1.5 Hz), 4.73 (d, 1H,
J = 5.0 Hz), 2.61-2.51 (m, 1H), 2.47 (br s, 1H), 0.94 (d, 3H, J = 7.0
Hz).
13C NMR (CDCl3, 100 MHz): d = 149.99, 146.91, 139.25, 127.15,
123.11, 116.39, 75.97, 44.51, 13.34.
1H NMR (CDCl3, 400 MHz): d = 7.36-7.26 (m, 5H), 5.93-5.82 (m,
1H), 5.14-5.07 (m, 2H), 4.62 (d, 1H, J = 5.0 Hz), 3.75 (m, 1H),
2.35-2.27 (m, 1H), 2.18-2.09 (m, 1H), 2.00 (d, 1H, J = 4.5 Hz),
0.93 (s, 9H), 0.08 (s, 3H), -0.14 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 141.13, 135.19, 127.99, 127.53,
127.01, 117.25, 77.68, 75.19, 36.34, 25.75, 18.09, -4.68, -5.11.
MS (CI-): m/z = 293 (MH+, 11), 292 (M+, 33), 291 ((M-H)-, 100),
233 (8), 159 (22), 131 (46), 119 (29).
MS (EI): m/z = 207 (M+, 1), 153 (20), 152 (100), 122 (20), 106 (30),
105 (24), 94 (30).
HRMS (CI-): m/z calcd for C17H27O2Si (M-H)- 291.1780. Found:
291.1769.
HRMS (EI): m/z calcd for C11H13NO3 207.0895. Found: 207.0882.
(1S*,2S*)-2-Methyl-1-(4-Nitrophenyl)but-3-en-1-ol (5h)
IR (NaCl, thin film): n = 3419, 3120, 2988, 2910, 1665, 1609, 1520,
1350, 1059, 922, 855, 754, 700 cm-1.
1H NMR (CDCl3, 400 MHz): d = 8.16 (d, 2H, J = 9.0 Hz), 7.48 (d,
2H, J = 8.5 Hz), 5.72 (ddd, 1H, J = 17.0, 10.5, 8.0 Hz), 5.20-5.12
(m, 2H), 4.51 (d, 1H, J = 7.0 Hz), 2.49 (br s, 1H), 2.44 (sextet, 1H,
J = 7.0 Hz), 0.91 (d, 3H, J = 7.0 Hz).
13C NMR (CDCl3, 100 MHz): d = 149.83, 147.20, 139.08, 127.50,
123.27, 117.74, 76.66, 46.21, 16.17.
MS (EI): m/z = 207 (M+, 1), 153 (25), 152 (100), 122 (15), 106 (24),
105 (17), 94 (17).
(2R*,3S*,4R*)-2-(tert-Butyldimethylsilanyloxy)-4-methylhex-5-
en-3-ol (7c-"anti")
IR (NaCl, thin film): n = 3440, 2957, 2930, 2858, 1641, 1463, 1256,
1086, 1004, 969, 835, 776 cm-1.
1H NMR (CDCl3, 400 MHz): d = 5.64 (ddd, 1H, J = 17.5, 10.5, 8.5
Hz), 5.07-4.96 (m, 2H), 3.81 (dq, 1H, J = 6.0, 3.5 Hz), 3.31 (ddd,
1H, J = 8.5, 3.5, 2.0 Hz), 2.35 (d, 1H, J = 2.0 Hz), 2.30-2.14 (m,
1H), 1.08 (d, 3H, J = 6.5 Hz), 1.07 (d, 3H, J = 6.0 Hz), 0.87 (s, 9H),
0.04 (s, 3H), 0.03 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 140.37, 114.89, 78.18, 69.51,
40.24, 25.76, 17.95, 16.74, 16.01, -4.50, -4.96.
MS (CI-): m/z = 244 (M-, 23), 243 ((M-H)-, 100), 187 (45), 131
(55), 127 (24).
HRMS (EI): m/z calcd for C11H13NO3 207.0895. Found: 207.0887.
HRMS (CI-): m/z calcd for C13H27O2Si (M-H)- 243.1780. Found:
(2S*,3S*)-2-(tert-Butyldimethylsilanyloxy)hex-5-en-3-ol (7a-
"syn")17a
243.1779.
1H NMR (CDCl3, 400 MHz): d = 5.92-5.80 (m, 1H), 5.12-5.05 (m,
2H), 3.72-3.66 (m, 1H), 3.40-3.33 (m, 1H), 2.40 (d, 1H, J = 5.5
Hz), 2.29-2.11 (m, 2H), 1.15 (d, 3H, J = 6.5 Hz), 0.89 (s, 9H), 0.08
(s, 3H), 0.07 (s, 3H).
(2R*,3S*,4S*)-2-(tert-Butyldimethylsilanyloxy)-4-methylhex-5-
en-3-ol (7d-"anti")
1H NMR (CDCl3, 400 MHz): d = 5.90 (ddd, 1H, J = 17.0, 10.5, 7.5
Hz), 5.11-4.99 (m, 2H), 3.85 (dq, 1H, J = 6.5, 4.0 Hz), 3.31-3.26
(m, 1H), 2.27 (d, 1H, J = 3.5 Hz), 2.33-2.21 (m, 1H), 1.11 (d, 3H,
J = 6.5 Hz), 0.97 (d, 3H, J = 7.0 Hz), 0.87 (s, 9H), 0.06 (s, 3H), 0.05
(s, 3H).
13C NMR (CDCl3, 100 MHz): d = 135.13, 116.89, 75.11, 70.80,
38.03, 25.78, 20.10, 17.98, -4.16, -4.89.
(2R*,3S*)-2-(tert-Butyldimethylsilanyloxy)hex-5-en-3-ol (7a-
"anti")17a
13C NMR (CDCl3, 100 MHz): d = 140.89, 114.67, 78.35, 69.44,
39.10, 25.75, 17.95, 16.73, 16.02, -4.42, -4.94.
1H NMR (CDCl3, 400 MHz): d = 5.91-5.79 (m, 1H), 5.15-5.07 (m,
2H), 3.80-3.73 (m, 1H), 3.59-3.53 (m, 1H), 2.30-2.13 (m, 2H),
2.19 (d, 1H, J = 3.5 Hz), 1.10 (d, 3H, J = 6.5 Hz), 0.88 (s, 9H), 0.07
(s, 3H), 0.06 (s, 3H).
(2S*,3S*,4S*)-2-(tert-Butyldimethylsilanyloxy)-4-methylhex-5-
en-3-ol (7d-"syn")
IR (NaCl, thin film): n = 3440, 3076, 2958, 2931, 2897, 2859, 1641,
13C NMR (CDCl3, 100 MHz): d = 135.03, 117.29, 74.43, 70.80,
36.72, 25.76, 17.98, 17.28, -4.46, -4.90.
MS (CI-): m/z = 231 (MH+, 8), 230 (M+, 27), 229 ((M-H)-, 100), 173
1472, 1463, 1389, 1375, 1362, 1256, 1092, 1039 cm-1.
1H NMR (CDCl3, 400 MHz): d = 5.87 (ddd, 1H, J = 17.0, 10.5, 8.5
Hz), 5.06-4.96 (m, 2H), 3.74 (pentet, 1H, J = 6.0 Hz), 3.31 (dd, 1H,
(6), 171 (9), 131 (33).
Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York

996
R. A. Batey et al.
PAPER
J = 5.5, 4.5 Hz), 2.41 (d, 1H, J = 4.5 Hz), 2.31-2.23 (m, 1H), 1.13
(d, 3H, J = 6.0 Hz), 1.07 (d, 3H, J = 7.0 Hz), 0.88 (s, 9H), 0.07 (s,
3H), 0.06 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 140.14, 114.74, 79.02, 69.69,
40.35, 25.77, 20.09, 17.95, 17.68, -4.03, -4.92.
MS (CI-): m/z = 244 (M-, 22), 243 ((M-H)-, 100), 187 (58), 131
(86), 127 (54).
J = 14.5, 6.5, 2.5), 1.49-1.42 (m, 1H), 0.88 (d, 3H, J = 6.5 Hz), 0.87
(s, 9H), 0.82 (d, 3H, J = 6.5 Hz), 0.08 (s, 3H), 0.04 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 134.89, 117.41, 75.68, 67.64,
42.55, 38.14, 32.82, 29.86, 19.18, 17.97, 17.64, -4.46, -4.61.
MS (CI-): m/z = 271 ((M-H)-, 18), 157 (6), 133 (9), 132 (15), 131
(100), 91 (7).
HRMS (CI-): m/z calcd for C15H31O2Si (M-H)- = 271.2093.
Found: 271.2107.
HRMS (CI-): m/z calcd for C13H27O2Si (M-H)- 243.1780. Found:
243.1778.
(1S*,3S*)-1-(tert-Butyldimethylsilanyloxy)-1-phenylhex-5-en-
3-ol (9b-"syn")
(1R*,2S*,3R*)-1-(tert-Butyldimethylsilanyloxy)-3-methyl-1-
phenylpent-4-en-2-ol (7e-"anti")
IR (NaCl, thin film): n = 3475, 3066, 3032, 2957, 2930, 2888, 2858,
1639, 1471, 1462, 1454, 1389, 1362, 1329, 1257, 1201, 1095, 1064,
1028, 1005, 913, 837, 864, 777, 700, 666 cm-1.
1H NMR (CDCl3, 400 MHz): d = 7.36-7.23 (m, 5H), 5.88-5.74 (m,
1H), 5.12-5.05 (m, 2H), 4.89 (dd, 1H, J = 10.0, 4.5 Hz), 3.91-3.80
(m, 1H), 3.48 (br s, 1H), 2.32-2.19 (m, 2H), 1.93-1.82 (m, 1H),
1.80-1.73 (m, 1H), 0.91 (s, 9H), 0.06 (s, 3H), -0.23 (s, 3H).
1H NMR (CDCl3, 400 MHz): d = 7.40-7.25 (m, 5H), 5.88 (ddd, 1H,
J = 17.0, 10.5, 7.5 Hz), 5.12-5.03 (m, 2H), 4.63 (d, 1H, J = 6.0 Hz),
3.66 (dt, 1H, J = 6.0, 3.0 Hz), 2.44-2.31 (m, 1H), 1.92 (d, 1H,
J = 3.0 Hz), 1.08 (d, 3H, J = 7.0 Hz), 0.90 (s, 9H), 0.06 (s, 3H),
-0.20 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 141.79, 141.11, 127.94, 127.67,
127.64, 114.75, 78.64, 75.87, 38.59, 25.78, 18.04, 14.04, -4.56,
-5.16.
MS (CI-): m/z = 306 (M-, 29), 305 ((M-H)-, 100), 173 (10), 131
(66), 127 (20), 119 (34).
HRMS (CI-): m/z calcd for C18H29O2Si (M-H)- 305.1937. Found:
305.1935.
13C NMR (CDCl3, 100 MHz): d = 144.64, 134.60, 128.20, 127.37,
125.89, 117.39, 76.15, 70.29, 46.51, 41.93, 25.72, 17.89, -4.51,
-5.16.
(1R*,3S*)-1-(tert-Butyldimethylsilanyloxy)-1-phenylhex-5-en-
3-ol (9b-"anti")
IR (NaCl, thin film): n = 3460, 2929, 2857, 1641, 1472, 1362, 1257,
1087, 1063, 914, 836, 777, 700, 666 cm-1.
1H NMR (CDCl3, 400 MHz): d = 7.36-7.20 (m, 5H), 5.87-5.72 (m,
1H), 5.11-5.07 (m, 2H), 5.05 (dd, 1H, J = 10.0, 4.5 Hz), 3.90-3.84
(m, 1H), 3.13 (br s, 1H), 2.26-2.18 (m, 2H), 1.81 (t, 2H, J = 5.0
Hz), 0.93 (s, 9H), 0.09 (s, 3H), -0.10 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 144.32, 134.74, 128.07, 126.95,
125.57, 117.29, 73.22, 67.23, 45.79, 42.08, 25.74, 18.04, -4.84,
-5.31.
MS (CI-): m/z = 306 (M-, 8), 305 ((M-H)-, 100), 173 (15).
HRMS (CI-): m/z calcd for C18H29O2Si (M-H)- = 305.1937.
Found: 305.1940.
(1R*,2S*,3S*)-1-(tert-Butyldimethylsilanyloxy)-3-methyl-1-
phenylpent-4-en-2-ol (7f-"anti")
IR (NaCl, thin film): n = 3578, 3071, 3032, 2957, 2930, 2887, 2858,
1639, 1494, 1472, 1463, 1454, 1388, 1361, 1317, 1257, 1160, 1079,
1065, 1005, 911, 864, 837, 778, 701 cm-1.
1H NMR (CDCl3, 400 MHz): d = 7.36-7.25 (m, 5H), 5.99 (ddd, 1H,
J = 17.5, 10.5, 7.5 Hz), 5.10 (dd, 1H, J = 10.5, 2.0 Hz), 4.99 (ddd,
1H, J = 17.5, 2.0, 1.0 Hz), 4.50 (d, 1H, J = 8.0 Hz), 3.53 (dt, 1H,
J = 8.0, 2.5 Hz), 2.89 (dd, 1H, J = 2.0, 1.0 Hz), 2.09-1.96 (m, 1H),
1.07 (d, 3H, J = 7.0 Hz), 0.89 (s, 9H), 0.04 (s, 3H), -0.25 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 141.50, 139.49, 128.13, 127.81,
127.33, 115.46, 79.52, 77.24, 38.83, 25.75, 18.75, 18.07, -4.46,
-5.12.
(1S*,3R*,4R*)-1-(tert-Butyldimethylsilanyloxy)-4-methyl-1-
phenylhex-5-en-3-ol (9c-"syn")
1H NMR (CDCl3, 400 MHz): d = 7.34-7.21 (m, 5H), 5.87-5.76 (m,
1H), 5.07-4.98 (m, 2H), 4.87 (dd, 1H, J = 7.5, 6.5 Hz), 3.70, (dd,
1H, J = 11.0, 5.5 Hz), 3.46 (br s, 1H), 2.32-2.18 (m, 1H), 1.90-
1.70 (m, 2H), 1.04 (d, 3H, J = 7.0 Hz), 0.91 (s, 9H), 0.06 (s, 3H),
-0.23 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 144.76, 140.81, 128.25, 127.43,
125.97, 114.81, 76.81, 74.54, 44.15, 43.75, 25.78, 17.94, 14.90,
-4.45, -5.10.
MS (CI-): m/z = 306 (M-, 33), 305 ((M-H)-, 100), 119 (57).
HRMS (CI-): m/z calcd for C18H29O2Si (M-H)- 305.1937. Found:
305.1936.
(1R*,3R*,4R*)-1-(tert-Butyldimethylsilanyloxy)-4-methyl-1-
phenylhex-5-en-3-ol (9c-"anti")
IR (NaCl, thin film): n = 3506, 3065, 3029, 2956, 2930, 2886, 2858,
1640, 1494, 1472, 1463, 1454, 1412, 1389, 1362, 1257, 1090, 1061,
1004, 914, 890, 837, 778, 701 cm-1.
1H NMR (CDCl3, 400 MHz): d = 7.34-7.21 (m, 5H), 5.75-5.62 (m,
1H), 5.09 (dd, 1H, J = 6.5, 3.5 Hz), 5.06-4.97 (m, 2H), 3.65 (ddd,
1H, J = 6.5, 6.0, 2.0 Hz), 2.98 (br s, 1H), 2.32-2.18 (m, 1H), 1.90-
1.70 (m, 2H), 1.01 (d, 3H, J = 7.0 Hz), 0.94 (s, 9H), 0.09 (s, 3H),
-0.10 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 144.38, 140.92, 128.09, 126.94,
125.60, 114.86, 73.33, 71.20, 43.93, 43.41, 25.78, 18.08, 15.03,
-4.78, -5.30.
(3S*,5S*)-3-(tert-Butyldimethylsilanyloxy)-2-methyloct-7-en-5-
ol (9a-"syn")
1H NMR (CDCl3, 400 MHz): d = 5.85-5.75 (m, 1H), 5.10-5.04 (m,
2H), 3.80-3.74 (m, 2H), 3.16 (d, 1H, J = 1.5 Hz), 2.25-2.13 (m,
2H), 1.84-1.75 (m, 1H), 1.52-1.46 (m, 2H), 0.88 (s, 9H), 0.86 (d,
3H, J = 6.5 Hz), 0.80 (d, 3H, J = 6.5 Hz), 0.08 (s, 3H), 0.06 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 134.87, 117.30, 77.11, 70.18,
42.05, 36.49, 33.37, 25.81, 18.16, 17.94, 15.86, -4.20, -4.73.
(3R*,5S*)-3-(tert-Butyldimethylsilanyloxy)-2-methyloct-7-en-5-
ol (9a-"anti")
IR (NaCl, thin film): n = 3442, 3077, 2957, 2857, 1641, 1472, 1386,
1256, 1068, 1005, 915, 835, 775, 665 cm-1.
MS (CI-): m/z = 320 (M-, 19), 319 ((M-H)-, 62), 205 (25), 131
(35), 127 (100).
HRMS (CI-): m/z calcd for C19H31O2Si (M-H)- 319.2093. Found:
319.2087.
1H NMR (CDCl3, 400 MHz): d = 5.85-5.76 (m, 1H), 5.11-5.04 (m,
2H), 3.96-3.87 (m, 1H), 3.66 (dt, 1H, J = 6.5, 3.0), 2.93 (d, 1H,
J = 2.5 Hz), 2.23-2.16 (m, 2H), 1.87-1.77 (m, 1H), 1.60 (ddd, 1H,
Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Diastereoselective Allylation and Crotylation Reactions of Aldehydes
997
(1S*, 3R*, 4S*)-1-(tert-Butyldimethylsilanyloxy)-4-methyl-1-
phenylhex-5-en-3-ol (9d-"syn")
(e) Batey, R. A.; Thadani, A. N.; Lough, A. J. Chem. Commun.
1999, 475.
1H NMR (CDCl3, 400 MHz): d = 7.37-7.22 (m, 5H), 5.81 (ddd, 1H,
J = 17.0, 10.5, 8.0 Hz), 5.10-5.00 (m, 2H), 4.89 (dd, 1H, J = 9.0,
4.5 Hz), 3.72-3.64 (m, 1H), 3.32 (br s, 1H), 2.32-2.22 (m, 1H),
1.91-1.70 (m, 2H), 1.03 (d, 3H, J = 7.0 Hz), 0.91 (s, 9H), 0.06 (s,
3H), -0.22 (s, 3H).
(f) Batey, R. A.; Smil, D. V. Tetrahedron Lett. 1999, 40, 9183.
(6) Batey, R. A.; Thadani, A. N.; Smil, D. V. Tetrahedron Lett.
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(7) (a) Vedejs, E.; Chapman, R. W.; Fields, S. C.; Lin, S.;
Schrimpf, M. R. J. Org. Chem. 1995, 60, 3020; and references
therein.
13C NMR (CDCl3, 100 MHz): d = 144.82, 140.30, 128.24, 127.40,
126.00, 115.17, 76.39, 74.20, 44.06, 43.70, 25.76, 17.92, 15.17,
-4.50, -5.13.
(b) Vedejs, E.; Fields, S. C.; Hayashi, R.; Hitchcock, R.;
Powell, D. R.; Schrimpf, M. R. J. Am. Chem. Soc. 1999, 121,
2460.
(c) Petasis, N. A.; Yudin, A. K.; Zavialov, I. A.; Prakash, G.
K. S.; Olah, G. A. Synlett 1997, 606.
(d) Darses, S.; Michaud, G.; Genêt, J. -P. Eur. J. Org. Chem.
1999, 1875.
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(f) Darses, S.; Michaud, G.; Genêt, J. -P. Tetrahedron Lett.
1998, 39, 5045.
(1R*,3R*,4S*)-1-(tert-Butyldimethylsilanyloxy)-4-methyl-1-
phenylhex-5-en-3-ol (9d-"anti")
1H NMR (CDCl3, 400 MHz): d = 7.37-7.22 (m, 5H), 5.77 (ddd, 1H,
J = 17.0, 10.5, 8.0 Hz), 5.11-5.00 (m, 3H), 3.70-3.62 (m, 1H), 2.85
(br s, 1H), 2.20-2.10 (m, 1H), 1.86-1.73 (m, 2H), 1.00 (d, 3H,
J = 7.0 Hz), 0.93 (s, 9H), 0.08 (s, 3H), -0.10 (s, 3H).
13C NMR (CDCl3, 100 MHz): d = 144.61, 140.48, 128.24, 126.92,
125.62, 115.35, 73.05, 71.01, 44.06, 43.79, 25.76, 18.07, 15.82, -
4.82, -5.33.
MS (CI-): m/z = 320 (M-, 7), 319 ((M-H)-, 27), 205 (24), 131
(100), 127 (47).
HRMS (CI-): m/z calcd for C19H31O2Si (M-H)- = 319.2093;
found = 319.2077.
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IR (NaCl, thin film): n = 3506, 3065, 3029, 2956, 2929, 2886, 2858,
1640, 1473, 1462, 1454, 1413, 1389, 1362, 1257, 1090, 1060, 837,
778 cm-1.
Acknowledgement
(12) For reactions involving other allyl- or crotylboron reagents,
see: (a) Hoffmann, R. W.; Metternich, R.; Lanz, J. W. Liebigs
Ann. Chem. 1987, 881.
†
Author to whom correspondence regarding the crystallographic
data should be addressed.
(b) Brinkmann, H.; Hoffmann, R. W. Chem. Ber. 1990, 123,
2395.
This work was supported by the Natural Science and Engineering
Research Council (NSERC) of Canada. A.N.T. thanks the NSERC
of Canada for a postgraduate scholarship. R.A.B gratefully acknow-
ledges AstraZeneca, AstraZeneca R&D Montréal, Bio-Méga/Boe-
hringer Ingelheim Recherche Inc., the Environmental Science and
Technology Alliance of Canada, Merck-Frosst, the Ontario Rese-
arch and Development Challenge Fund, and Uniroyal Chemicals
Inc. for additional support. We thank Dr. A. B. Young for mass
spectroscopic analyses.
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Synthesis 2000, No. 7, 990–998 ISSN 0039-7881 © Thieme Stuttgart · New York