Asymmetric dehydrative C-, N-, and O-allylation using Naph-diPIM-dioxo-i- Pr-CpRu/p-TsOH combined catalyst

Article abstract of DOI:10.1055/s-0031-1290301

(S,S)- or (R,R)-Naph-diPIM-dioxo-i-Pr-CpRu(II) complex with a Bronsted acid catalyzes dehydrative intermolecular C-allylation with high enantio- and regioselectivity. The new soft Ru/hard H⁺ combined catalyst can also be used for intramolecular C-, N-, and O-allylations, giving nearly enantiomerically pure α-alkenyl-substituted cyclic compounds. As water is only the co-product, the synthetic process can be readily scaled up. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0031-1290301

2138▌
PRACTICAL SYNTHETIC PROCEDURES
pArasctyicaml symntheetticrpircoceDduerehs ydrative C-, N-, and O-Allylation Using Naph-diPIM-dioxo-
i-Pr–CpRu/p-TsOH Combined Catalyst
Asymmetric Dehydrative C-, N-, and O-Allylation
Kengo Miyata, Masato Kitamura*
Research Center for Materials Science and Department of Chemistry, Nagoya University, Chikusa,
Nagoya 464-8602, Japan
PSP
Fax +81(52)7892958; E-Mail: kitamura@os.rcms.nagoya-u.ac.jp
Received: 26.12.2011; Accepted after revision: 01.02.2012
No226
Abstract: (S,S)- or (R,R)-Naph-diPIM-dioxo-i-Pr–CpRu(II) complex with a Brønsted acid catalyzes dehydrative intermolecular
C-allylation with high enantio- and regioselectivity. The new soft Ru/hard H+ combined catalyst can also be used for intramolecular C-, N-,
and O-allylations, giving nearly enantiomerically pure α-alkenyl-substituted cyclic compounds. As water is only the co-product, the syn-
thetic process can be readily scaled up.
Key words: dehydrative allylation, asymmetric catalysis, cyclopentadienyl ruthenium, chiral bidentate sp2N ligand
procedure 1
Naph-diPIM-dioxo-i-Pr–CpRu/p-TsOH catalyst
O
O
O
O
+
–
PF6
cat*
(0.1 mol%)
O
O
OH
O
O
p-TsOH
O
O
+
+
CH2Cl2
reflux, 4 h
N
N
*
O
O
N
N
(E)-3a
4a
5a
Ru
6a
S
S
O
O
96% yield
>200:1 B/L
>99:1 er
500 mM
2500 mM
O
O
O
O
(S,S)-1
(R,R)-1
+
–
PF6
p-TsOH
procedure 2
O
O
O
O
cat*
(0.1 mol%)
O
O
O
R
R
O
O
Ru
CH2Cl2
reflux, 1 h
N
N
*
N
N
O
OH
7a
1 M
98% yield
>99:1 er
cat* = (S,S)- or (R,R)-1
Scheme 1
the asymmetric Tsuji–Trost reaction has realized the syn-
thesis of various natural products and is now a core reac-
Introduction
Geuther–Wislicenus alkylation of 1,3-dicarbonyl com- tion in organic synthesis.5 The only disadvantage is that
pounds has been one of the most frequently utilized C–C enolate formation using a base is required for the reaction
bond formations in organic synthesis since its discovery in with activated allylic alcohols, such as allyl halides and
1863.1 Tsuji revolutionized this chemistry by using palla- esters. An ideal reaction would be direct C–C bond forma-
dium-catalyzed allylation in 1965,2 and then Trost report- tion from 1,3-dicarbonyl compounds and allylic alcohols
ed the first asymmetric version in 1977.3 The reports have by the liberation of water (Scheme 1, procedure 1). This
spurred subsequent research on related chemistry, which can be realized using a monocationic CpRu(II) complex
mainly utilizes various chiral phosphine–Pd complexes of a new type of chiral bisamidine ligand with a naph-
and others, including Mo, Ru, Rh, W, and Ir complexes.4 tho[1,2-b:7,8-b′]dipyrroloimidazole (Naph-diPIM) skele-
Coupled with the high synthetic utility of the allyl group, ton in combination with a Brønsted acid (Naph-diPIM-
dioxo-i-Pr–CpRu(II)/p-TsOH [(S,S)- and (R,R)-1]. The
new system, which has been designed on the basis of the
‘redox-mediated donor-acceptor bifunctional catalyst
(RDACat)’ concept, shows high efficiency in asymmetric
SYNTHESIS 2012, 44, 2138–2146
Advanced online publication: 03.04.2012
DOI: 10.1055/s-0031-1290301; Art ID: SS-2012-Z1187-PSP
© Georg Thieme Verlag Stuttgart · New York
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X

PRACTICAL SYNTHETIC PROCEDURES
Asymmetric Dehydrative C-, N-, and O-Allylation
2139
dehydrative allylation. Particularly, intramolecular C-, N-, ing substituents as well as the electron-withdrawing nitro
and O-allylations have opened new practical routes to group could be introduced at the para-position of the phe-
near enantiomerically pure cycloalkanes and N- and O- nyl group of (E)-3b–e (entries 3–6). An alkenyl 3f or al-
heterocycles (Scheme 1, procedure 2).6,7
kynyl group at C3 3g instead of a phenyl group was
tolerated, giving the corresponding branched products
5f,g, respecitively, with 96:4–99:1 er (entries 7 and 8).
Both (E)-3a and (Z)-3a and racemic 1-phenylprop-2-en-
1-ol (3h) were converted into (S)-5a, implying that π–σ–π
Scope and Limitations
Under the conditions (S,S)-Naph-diPIM-dioxo-i-Pr (5 interconversion should be faster than the intermolecular
mM), [CpRu(MeCN)3]PF6 (2) (5 mM), p-TsOH (5 mM), nucleophilic attack on a possible intermediary π-allyl–
cinnamyl alcohol [(E)-3a] (500 mM), and Meldrum’s acid Ru(IV) complex. 5-Methyl-Meldrum’s acid (4b), tetronic
(4a) (2500 mM), in dichloromethane at reflux for one acid (4c), and 3-methyltetronic acid (4d) can be also used
hour, the branched monoallyl product (S)-5a with >99:1 as C-nucleophiles. 3-Methyltetronic acid (4d) gave a near
S/R er was obtained in 96% isolated yield (Table 1 entry 1:1 diastereomer mixture with high enantiocontrol at the
1). The ratio of 5a and linear isomer 6a [branch/linear allylic carbon. No reaction occurred with dimethyl malo-
(B/L)] is >200:1. A decrease in the catalyst concentration nate 4e under the present reaction conditions (entry 16).
to 0.5 mM [substrate/catalyst (S/C) ratio = 1000] exerted Introduction of a methyl substituent at C3 (E)-3j led to no
little negative effect on the S/R and B/L ratios, although detectable reaction (entry 15), and saturation of the phenyl
four hours were required for full conversion. By changing group of (E)-3i caused β-elimination to give a diene prod-
the chirality of catalyst from (S,S)-1 to (R,R)-1, enantio- uct (entry 14).
meric (R)-5a was also produced (entry 2). Electron-donat-
Table 1 Intermolecular Enantioselective Dehydrative Allylation Using (S,S)-Naph-diPIM-dioxo-i-Pr/[CpRu(MeCN)3]PF6/p-TsOH Com-
bined Catalysta
Entry
Allylic alcohol
1,3-Dione
Product
Isolated yield (%) (er)
O
O
O
O
O
Ph
OH
O
1
96 (>99:1)
O
O
(E)-3a
Ph
4a
(S)-5a
b
O
O
O
O
2
(E)-3a
4a
96 (1:>99)
Ph
(R)-5a
O
O
O
R
OH
O
*
R
R = 4-MeOC6H4 (E)-3b
R = 4-MeC6H4 (E)-3c
R = 4-ClC6H4 (E)-3d
R = 4-O2NC6H4 (E)-3e
95 (98:2)
96 (99:1)
94 (99:1)
–c (99:1)
3
4
5
6
4a
4a
4a
4a
5b
5c
5d
5e
R = CH=CMe2 3f
R = C≡CPh 3g
7
8
4a
4a
5f
73 (96:4)
89 (99:1)
5g
O
O
Ph
O
O
93 (97:3)d
9
4a
OH
Ph
(Z)-3a
(S)-5a
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2138–2146

2140
K. Miyata, M. Kitamura
PRACTICAL SYNTHETIC PROCEDURES
Table 1 Intermolecular Enantioselective Dehydrative Allylation Using (S,S)-Naph-diPIM-dioxo-i-Pr/[CpRu(MeCN)3]PF6/p-TsOH Com-
bined Catalysta (continued)
Entry
10
Allylic alcohol
1,3-Dione
Product
Isolated yield (%) (er)
96 (96:4)d
OH
4a
(S)-5a
Ph
3h
O
O
O
O
O
O
Ph
OH
O
11
12
87 (99:1)
O
O
(E)-3a
*
Ph
4b
5h
O
O
O
HO
89 (>99:1)e
O
O
O
(E)-3a
(E)-3a
Ph
*
4c
5i
O
*
O
O
O
88 (95:5, 95:5)f
13
14
*
Ph
4d
5j
OH
g
4a
4a
–
–
(E)-3i
Ph
OH
15
16
–
–
no reaction
(E)-3j
O
O
h
(E)-3e
–
MeO
OMe
4e
a Reaction conditions: 1.0 mmol scale; allyl alcohol 3 (500 mM), 4 (2500 mM), 2 (5 mM), (S,S)-Naph-diPIM-dioxo-i-Pr (5 mM), p-TsOH (5
mM), CH2Cl2, reflux, 1 h. The absolute configurations were not determined unless otherwise specified.
b (R,R)-1 was used.
c Quantitative by 1H NMR analysis, but difficult in separation from 4a. Isolated as ethyl 3-(4-nitrophenyl)pent-4-enoate in 72% yield.
d Five times more diluted than the standard.
e HPLC analysis after acetylation.
f Diastereomeric ratio: ca. 1:1. 96:4 and 94:6 ers are also possible.
g Major product: allylidenecyclohexane.
h Major product: dicinnamyl ether.
Table 2 shows some examples of the intramolecular ver- reaction proceeds with an S/C ratio of 1000–10000. Not
sion. Intramolecular C-allylation using 7a–c quantitative- only N-tosyl but also N-Boc can be utilized, enhancing the
ly afforded the 2,3-dihydro-1H-indene 8a,b and 1,2,3,4- synthetic utility. The C3 aliphatic 7j–l, having no cin-
tetrahydronaphthalene derivatives 8c with >99:1 er in all namyl alcohol unit, are poor substrates (entries 13–15) for
cases (entries 1–3). Not only C-nucleophiles, but also N- the Naph-diPIM-dioxo-i-Pr–CpRu/p-TsOH catalyst sys-
and O-nucleophiles, can be used in the intramolecular cy- tem. Efficient dehydrative cyclization of aliphatic allylic
clization of 7d–i to give isoindoline 8d, 1,2,3,4-tetrahy- alcohols can be attained by use of another CpRu(II) com-
droisoquinoline 8e,f, phthalan 8g, and isochromane plex with Cl-Naph-PyCO2H [6-(2-chloronaphthalen-1-
derivatives 8h,i quantitatively with high enantioselectivi- yl)-5-methylpyridine-2-carboxylic acid] or its allyl ester.8
ty (entries 4–12). In most intramolecular cyclizations the
Synthesis 2012, 44, 2138–2146
© Georg Thieme Verlag Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES
Asymmetric Dehydrative C-, N-, and O-Allylation
2141
Table 2 Intramolecular Enantioselective Dehydrative Allylation Using (S,S)-Naph-diPIM-dioxo-i-Pr/[CpRu(MeCN)3]PF6/p-TsOH Com-
bined Catalysta
Entry
Reactant
Product
Isolated yield (%) (er)
O
O
O
O
O
O
O
O
1
98 (>99:1)
OH
(R)-8a
7a
O
O
O
O
O
O
O
O
98 (>99:1)b
2
*
OH
8b
7b
O
O
O
O
O
O
*
3
4
97 (>99:1)
99 (>99:1)
O
O
OH
8c
7c
NHTs
NTs
OH
(R)-8d
7d
NHTs
NTs
99 (99:1)
95 (99:1)c
83 (95:5)d
5
6
7
*
OH
8e
7e
NHBoc
NBoc
96 (>99:1)b
89 (99:1)
*
8
OH
8f
7f
OH
O
*
9
OH
OH
8g
7g
OH
O
98 (>99:1)
93 (94:6)c
10
11
(R)-8h
7h
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2138–2146

2142
K. Miyata, M. Kitamura
PRACTICAL SYNTHETIC PROCEDURES
Table 2 Intramolecular Enantioselective Dehydrative Allylation Using (S,S)-Naph-diPIM-dioxo-i-Pr/[CpRu(MeCN)3]PF6/p-TsOH Com-
bined Catalysta (continued)
Entry
Reactant
Product
Isolated yield (%) (er)
94 (99:1)b
OH
O
12
*
OH
8i
7i
O
O
O
O
O
O
57 (88:12)b,e
O
13
*
O
OH
8j
7j
NHTs
NTs
*
97 (82:18)b
14
15
OH
OH
8k
8l
7k
OH
O
*
–
b,f (60:40)
7l
a Reaction conditions: 1.0 mmol scale; substrate 7 (1 M), 2 (1.0 mM), (S,S)-Naph-diPIM-dioxo-i-Pr (1.0 mM), p-TsOH (1.0 mM), CH2Cl2, re-
flux, 1 h. The absolute configurations were not determined unless otherwise specified.
b S/C = 100; (S,S)-Naph-diPIM-dioxo-i-Pr (10 mM), p-TsOH (10 mM).
c S/C = 5000; 7 (1 M), 2 (0.2 mM), (S,S)-Naph-diPIM-dioxo-i-Pr (0.2 mM), p-TsOH (0.4 mM), 6 h.
d S/C = 10000; 7 (1 M), 2 (0.1 mM), (S,S)-Naph-diPIM-dioxo-i-Pr (0.1 mM), p-TsOH (0.4 mM), 12 h.
e A 61:39 mixture of (Z)- and (E)-5-(hexa-3,5-dienyl)-2,2-dimethyl-1,3-dioxane-4,6-dione was isolated in 13% yield.
f Not isolated. Quantitative by GC analysis.
Experimental Procedures
1 was confirmed by 1H NMR analysis. The 10 mM (S,S)-1 soln was
used for the reaction. A soln of p-TsOH·H2O (10 mM in MeOH,
0.10 mL, 1.0 μmol) was added to a 20-mL Young-type Schlenk, and
the soln was concentrated in vacuo. To this was added the (S,S)-1
soln (10 mM in acetone-d6, 0.10 mL, 1.0 μmol). After concentration
of the mixture in vacuo, cinnamyl alcohol (E-3a, 500 mM in
CH2Cl2, 2.0 mL, 134.2 mg, 1.00 mmol) and Meldrum’s acid (4a,
720.6 mg, 5.00 mmol) were introduced. After freezing the mixture
followed by evacuation, the whole system was closed. The yellow
soln was stirred for 4 h in a 60 °C oil bath, and then cooled to r.t.
After removal of all of volatiles in vacuo, the residue was purified
by column chromatography (silica gel, 50 g, EtOAc–hexane, 1:5) to
give (S)-5a as a white solid; yield: 249.9 mg (96%); er S/R 99.5:0.5
[HPLC analysis (5 mm φ × 250 mm Chiralpak AD-H; hexane–i-
PrOH, 1.0 mL/min flow rate; 220-nm detection, 27 °C): tR = 26.5
(R), 32.5 min (S)]. [a]D21 –50.7 (c 1.0, CHCl3) {[a]D20 51.5 (c 1.0,
CHCl3) for (R)-5a obtained with (R,R)-1}.
All reactions were carried out an under argon atmosphere using
general Schlenk techniques unless otherwise specified. A Schlenk
tube with Teflon J. Young valve was specified by ‘Young-type
Schlenk’. Schlenk tubes were dried at ca. 250 °C using a heat gun
under a reduced pressure. A Teflon-coated magnetic bar was used
for stirring the reaction mixture. Liquid reagents were introduced by
use of a syringe via a septum rubber. After introduction, the septum
was replaced with a Young valve. Heating in a closed system was
carried out after raising the temperature followed by closing the sys-
tem. Cannulation was performed by use of a Teflon tube or a stain-
less tube through a septum rubber under a slightly positive pressure
of argon. Solvents after general workup process were removed us-
ing a rotary evaporator. The concentration of a reaction mixture in
a Schlenk tube was performed by connecting to a vacuum–argon
line via a cold trap.
(S)-2,2-Dimethyl-5-[1-phenylallyl]-1,3-dioxane-4,6-dione [(S)-
5a]; Typical Procedure for Intermolecular Allylation (Table 1)
S/C 1000: Chiral ligand (S,S)-Naph-diPIM-dioxo-i-Pr (5.45 mg,
10.0 μmol) and acetone-d6 (0.50 mL) were added to a 5-mm Young-
type NMR tube. To another 5-mm Young-type NMR tube were
added [CpRu(MeCN)3]PF6 (2) (4.34 mg, 10.0 μmol) and acetone-d6
(0.50 mL). The soln of 2 was transferred to the soln of (S,S)-Naph-
diPIM-dioxo-i-Pr. After shaking for 10 min, the formation of (S,S)-
S/C 100: E-3a (500 mM in CH2Cl2, 2.0 mL, 134.2 mg, 1.00 mmol),
4a (720.6 mg, 5.00 mmol), the solns of 40 mM (S,S)-Naph-diPIM-
dioxo-i-Pr (0.250 mL, 10.0 μmol), 40 mM 2 (0.250 mL, 10.0 μmol),
and 40 mM p-TsOH·H2O (0.250 mL, 10.0 μmol) were used.
1
The H and 13C NMR spectra were consistent with the reported
data.9
Synthesis 2012, 44, 2138–2146
© Georg Thieme Verlag Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES
Asymmetric Dehydrative C-, N-, and O-Allylation
2143
5-[1-(4-Methoxyphenyl)allyl]-2,2-dimethyl-1,3-dioxane-4,6-di-
one (5b)
Yellow solid; yield 275.6 mg (95%); er 97.7:2.3 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99:1, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 48.8, 56.8 min].
HRMS (FAB): m/z [M+] calcd for C15H15NO6: 305.0899; found:
305.0898.
2,2-Dimethyl-5-(5-methylhexa-1,4-dien-3-yl)-1,3-dioxane-4,6-
dione (5f)
Pale yellow oil; yield: 133.9 mg (73%); er 95.7:4.3 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99.5:0.5, 0.5
mL/min flow rate, 220-nm detection, 27 °C): tR = 48.8, 54.6 min].
[α]D22 –51.5 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.46 (s, 3 H, CH3), 1.70 (s, 3 H, CH3), 3.78
(s, 3 H, ArOCH3), 3.83 [d, JH,H = 2.75 Hz, 1 H, COCH(CH)CO],
4.51 (dd, JH,H = 2.75, 8.26 Hz, 1 H, ArCH), 5.24 (d, JH,H = 10.33 Hz,
1 H, CH=CHH), 5.25 (d, JH,H = 17.21 Hz, 1 H, CH=CHH), 6.51
(ddd, JH,H = 8.26, 10.33, 17.21 Hz, 1 H, CHCH=CH2), 6.84 (d,
[α]D22 –39.1 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.69 (s, 3 H, C=CCH3), 1.73 [s, 6 H,
C(CH3)2], 1.74 (s, 3 H, C=CCH3), 3.55 [d, JH,H = 2.07 Hz, 1 H,
COCH(CH)CO], 4.09–4.12 [m, 1 H, C=CHCH(CH)CH=CH2],
5.09 (d, JH,H = 10.33 Hz, 1 H, CH=CHH), 5.18 (d, JH,H = 17.21 Hz,
1 H, CH=CHH), 5.42 [d, JH,H = 9.64 Hz, 1 H, (CH3)2C=CHCH],
6.00 (ddd, JH,H = 7.23, 10.33, 17.21 Hz, 1 H, CHCH=CH2).
JH,H = 8.94 Hz, 2 H, ArH), 7.28 (d, JH,H = 8.94 Hz, 2 H, ArH).
13C NMR (CDCl3): δ = 28.00, 28.43, 47.92, 52.62, 55.41, 105.39,
114.16, 117.91, 130.00, 131.49, 137.38, 159.01, 164.64, 164.87.
HRMS (FAB): m/z [M+] calcd for C16H18O5: 290.1154; found:
290.1142.
13C NMR (CDCl3): δ = 18.21, 26.07, 27.69, 41.98, 51.55, 105.11,
116.73, 121.78, 136.07, 137.43, 164.67, 164.76.
5-[1-(4-Methylphenyl)allyl]-2,2-dimethyl-1,3-dioxane-4,6-di-
one (5c)
White solid; yield: 262.3 mg (96%); er 99.0:1.0 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99:1, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 31.0, 38.5 min].
HRMS (FAB): m/z [M+] calcd for C13H18O4: 238.1205; found:
238.1204.
2,2-Dimethyl-5-(5-phenylpent-1-en-4-yn-3-yl)-1,3-dioxane-4,6-
dione (5g)
Pale yellow solid; yield: 252.0 mg (89%); er 98.6:1.4 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99:1, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 48.8, 72.9 min].
[α]D22 –53.4 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.47 (s, 3 H, CH3), 1.70 (s, 3 H, CH3), 2.31
(s, 3 H, ArCH3), 3.85 [d, JH,H = 2.75 Hz, 1 H, COCH(CH)CO], 4.52
(dd, JH,H = 2.75, 8.26 Hz, 1 H, ArCH), 5.25 (d, JH,H = 8.95 Hz, 1 H,
CH=CHH), 5.27 (d, JH,H = 17.21 Hz, 1 H, CH=CHH), 6.50 (ddd,
[α]D23 –118.1 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.78 (s, 3 H, CH3), 1.79 (s, 3 H, CH3), 3.80
[d, JH,H = 2.75 Hz, 1 H, COCH(CH)CO], 4.42–4.44 (m, 1 H,
CCCH), 5.31 (d, JH,H = 10.33 Hz, 1 H, CH=CHH), 5.53 (d,
J
H,H = 8.26, 8.95, 17.21 Hz, 1 H, CHCH=CH2), 7.12 (d, JH,H = 8.26
Hz, 2 H, ArH), 7.24 (d, JH,H = 8.26 Hz, 2 H, ArH).
J
H,H = 17.21 Hz, 1 H, CH=CHH), 6.12 (ddd, JH,H = 9.64, 10.33,
13C NMR (CDCl3): δ = 21.16, 27.96, 28.41, 48.16, 52.51, 105.38,
118.20, 128.64, 129.48, 136.54, 137.11, 137.25, 164.64, 164.72.
HRMS (FAB): m/z [M+] calcd for C16H18O4: 274.1205; found:
274.1216.
17.21 Hz, 1 H, CH=CH2), 7.25–7.29 (m, 3 H, PhH), 7.41–7.43 (m,
2 H, PhH).
13C NMR (CDCl3): δ = 27.64, 28.59, 35.50, 51.27, 85.04, 85.87,
105.43, 119.06, 122.86, 128.33, 128.46, 131.99, 133.84, 163.33,
163.56.
HRMS (FAB): m/z [M+] calcd for C17H16O4: 284.1049; found:
284.1053.
5-[1-(4-Chlorophenyl)allyl]-2,2-dimethyl-1,3-dioxane-4,6-di-
one (5d)
Pale yellow solid; yield: 275.9 mg (94%); er 98.8:1.2 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99:1, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 39.5, 48.1 min].
2,2,5-Trimethyl-5-(1-phenylallyl)-1,3-dioxane-4,6-dione (5h)
White solid; yield: 239.2 mg (87%); er 98.9:1.1 [HPLC (5 mm
φ × 250 mm Chiralcel OJ–H, hexane–i-PrOH, 99:1, 0.5 mL/min
flow rate, 220-nm detection, 27 °C): tR = 40.1, 47.6 min].
[α]D22 –51.3 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.57 (s, 3 H, CH3), 1.73 (s, 3 H, CH3), 3.85
[d, JH,H = 2.75 Hz, 1 H, COCH(CH)CO], 4.52 (dd, JH,H = 2.75, 8.26
Hz, 1 H, ArCH), 5.275 (d, JH,H = 11.02 Hz, 1 H, CH=CHH), 5.28 (d,
JH,H = 15.84 Hz, 1 H, CH=CHH), 6.46 (ddd, JH,H = 8.26, 11.02,
15.84 Hz, 1 H, CHCH=CH2), 7.28 (d, JH,H = 8.26 Hz, 2 H, ArH),
7.31 (d, JH,H = 8.26 Hz, 2 H, ArH).
13C NMR (CDCl3): δ = 27.78, 28.41, 47.49, 52.31, 105.41, 118.87,
128.87, 130.31, 133.46, 136.43, 138.07, 164.31, 164.42.
HRMS (FAB): m/z [M+] calcd for C15H15ClO4: 294.0659; found:
294.0652.
[α]D21 –75.5 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 0.93 (s, 3 H, CH3), 1.58 (s, 3 H, CH3), 1.64
[s, 3 H, COC(CO)CH3C], 3.93 (d, JH,H = 9.97 Hz, 1 H, PhCH), 5.27
(dd, JH,H = 1.36, 17.18 Hz, 1 H, CH=CHH), 5.31 (dd, JH,H = 1.36,
10.31 Hz, 1 H, CH=CHH), 6.55 (ddd, JH,H = 9.97, 10.31, 17.18 Hz,
1 H, CHCH=CH2), 7.19 (d, JH,H = 6.87 Hz, 2 H, PhH), 7.24 (t,
JH,H = 6.87 Hz, 1 H, PhH), 7.29 (t, JH,H = 6.87 Hz, 2 H, PhH).
13C NMR (CDCl3): δ = 23.76, 27.83, 30.10, 54.30, 58.51, 105.37,
119.79, 128.05, 128.89, 129.01, 134.92, 138.90, 168.82, 170.42.
HRMS (ESI): m/z [M + Na+] calcd for C16H18NaO4: 297.1097;
found: 297.1087.
2,2-Dimethyl-5-[1-(4-nitrophenyl)allyl]-1,3-dioxane-4,6-dione
(5e)
The er was determined after converting into ethyl 3-(4-nitrophe-
nyl)pent-4-enoate.
4-Hydroxy-3-(1-phenylallyl)furan-2(5H)-one (5i)
White solid; yield: 192.3 mg (89%); the er was determined after
acetylation.
[α]D21 –54.5 (c 1.0, MeOH).
1H NMR (CD3OD): δ = 4.45 (d, JH,H = 8.25 Hz, 1 H, PhCH), 4.62
(s, 2 H, COCH2O), 5.099 (d, JH,H = 10.31 Hz, 1 H, CH=CHH),
5.100 (d, JH,H = 17.18 Hz, 1 H, CH=CHH), 6.40 (ddd, JH,H = 8.25,
10.31, 17.18 Hz, 1 H, CHCH=CH2), 7.15 (t, JH,H = 7.56 Hz, 1 H,
PhH), 7.24 (t, JH,H = 7.56 Hz, 2 H, PhH), 7.30 (d, JH,H = 7.56 Hz, 2
H, PhH).
1H NMR (CDCl3): δ = 1.67 (s, 3 H, CH3), 1.77 (s, 3 H, CH3), 3.93
[d, JH,H = 2.75 Hz, 1 H, COCH(CH)CO], 4.67 (dd, JH,H = 2.75, 8.95
Hz, 1 H, ArCH), 5.347 (d, JH,H = 17.90 Hz, 1 H, CH=CHH), 5.354
(d, JH,H = 10.33 Hz, 1 H, CH=CHH), 6.45 (ddd, JH,H = 8.95, 10.33,
17.90 Hz, 1 H, CHCH=CH2), 7.58 (d, JH,H = 8.26 Hz, 2 H, ArH),
8.17 (d, JH,H = 8.26 Hz, 2 H, ArH).
13C NMR (CDCl3): δ = 27.51, 28.38, 47.31, 51.99, 105.55, 120.19,
123.77, 129.87, 135.19, 147.19, 147.24, 163.93, 163.97.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2138–2146

2144
K. Miyata, M. Kitamura
PRACTICAL SYNTHETIC PROCEDURES
13C NMR (CD3OD): δ = 43.70, 68.04, 103.22, 115.91, 127.34,
128.76, 129.24, 139.00, 143.10, 175.30, 177.25.
Hz, 1 H, C=CHH), 7.08 (d, JH,H = 6.89 Hz, 1 H, ArH), 7.22–7.28
(m, 3 H, ArH).
HRMS (ESI): m/z [M + Na+] calcd for C13H12NaO3: 239.0679;
found: 239.0687.
13C NMR (CDCl3): δ = 21.45, 28.31, 30.41, 42.06, 60.57, 66.26,
105.17, 118.23, 124.11, 125.01, 127.32, 128.04, 140.02, 140.73,
141.50, 167.82, 171.16.
3-Methyl-3-(1-phenylallyl)furan-2,4(3H,5H)-dione (5j)
White solid; yield: 202.7 mg (88%); er 95:5 and 95:5 (or 96:4 and
94:6) [HPLC (5 mm φ × 250 mm Chiralpak AD-H, hexane–i-PrOH,
99:1, 1 mL/min flow rate, 220-nm detection, 27 °C): tR = 11.8, 13.3,
15.1, 26.4 min].
1H NMR (CDCl3): δ = 1.32 (s, 3 H, CH3), 1.35 (s, 3 H, CH3), 3.46
(d, JH,H = 16.53 Hz, 1 H, OCHHCO), 3.54 (d, JH,H = 10.33 Hz, 1 H,
OCHHCO), 3.64 (d, JH,H = 10.33 Hz, 1 H, OCHHCO), 3.78 (d,
HRMS (FAB): m/z [M+] calcd for C17H18O4: 286.1205; found:
286.1191.
2,2-Dimethyl-1′-vinyl-3′,4′-dihydro-1′H-spiro[[1,3]dioxane-
5,2′-naphthalene]-4,6-dione (8c)
White solid; yield: 278.6 mg (97%); er 99.9:0.1 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99:1, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 17.7, 19.4 min].
[α]D22 –169.4 (c 1.0, CHCl3).
J
H,H = 16.53 Hz, 1 H, OCHHCO), 4.31 (d, JH,H = 17.21 Hz, 1 H,
PhCH), 4.35 (d, JH,H = 17.21 Hz, 1 H, PhCH), 5.26 (d, JH,H = 17.21
Hz, H, 2 × CH=CHH), 5.31 (d, JH,H = 10.33 Hz, 2 H,
1H NMR (CDCl3): δ = 1.73 (s, 3 H, CH3), 1.76 (s, 3 H, CH3), 2.31
(ddd, JH,H = 4.12, 4.81, 13.75 Hz, 1 H, ArCH2CHHC), 2.47–2.53
(m, 1 H, ArCH2CHHC), 2.93 (ddd, JH,H = 4.67, 4.81, 16.70 Hz, 1 H,
ArCHHCH2C), 3.01–3.08 (m, 1 H, ArCHHCH2C), 4.32 (d,
2
2 × CH=CHH), 6.37 (ddd, JH,H = 10.33, 17.21, 17.21 Hz, 1 H,
CHCH=CH2), 6.46 (ddd, JH,H = 10.33, 17.21, 17.21 Hz, 1 H,
CHCH= CH2), 7.18 (d, JH,H = 7.57 Hz, 2 H, PhH), 7.20 (d,
J
H,H = 9.62 Hz, 1 H, ArCHC), 5.39 (d, JH,H = 17.18 Hz, 1 H,
CH=CHH), 5.40 (d, JH,H = 10.31 Hz, 1 H, CH=CHH), 5.83 (ddd,
H,H = 9.62, 10.31, 17.18 Hz, 1 H, CH=CHCH2), 7.13–7.19 (m, 3 H,
JH,H = 7.57 Hz, 2 H, PhH), 7.25–7.32 (m, 6 H, PhH).
13C NMR (CDCl3): δ = 18.95, 19.18, 52.66, 52.74, 56.26, 56.82,
72.72, 72.82, 119.83, 120.08, 128.14, 128.18, 128.28, 128.34,
129.06, 129.22, 133.43, 133.88 137.97, 176.29, 176.86, 210.69,
210.83.
HRMS (EI): m/z [M+] calcd for C14H14O3: 230.0943; found:
230.0933.
J
ArH), 7.25–7.27 (m, 1 H, ArH).
13C NMR (CDCl3): δ = 26.14, 29.28, 29.69, 32.33, 49.39, 54.30,
105.36, 122.08, 126.46, 126.48, 127.30, 128.16, 134.58, 135.32,
135.72, 166.32, 170.51.
HRMS (FAB): m/z [M+] calcd for C17H18O4: 286.1205; found:
286.1192.
(R)-2,2-Dimethyl-1′-vinyl-1′,3′-dihydrospiro[[1,3]dioxane-5,2′-
indene]-4,6-dione [(R)-8a]; Typical Procedure for Intramolecu-
lar Allylation (Table 2)
(R)-2-Tosyl-1-vinylisoindoline [(R)-8d]
White solid; yield: 295.8 mg (99%); er 99.5:0.5 [HPLC [5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 95:5, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 25.0 (R), 34.7 min (S)].
[α]D21 –127.6 (c 1.0, CHCl3).
The 10 mM (S,S)-Naph-diPIM-dioxo-i-Pr–CpRu soln and 10 mM
p-TsOH·H2O solns were prepared in the same way as that of inter-
molecular case. The 10 mM ligand/CpRu soln (0.10 mL, 1.0 μmol)
was introduced to a 20-mL Young-type Schlenk containing to p-
TsOH·H2O (1.0 μmol), and the soln was concentrated. To this was
added (E)-5-[2-(3-hydroxyprop-1-enyl)benzyl]-2,2-dimethyl-1,3-
dioxane-4,6-dione (7a) (1000 mM in CH2Cl2, 1.0 mL, 290.3 mg, 1.0
mmol). After freezing the mixture followed by evacuation, the
whole system was closed. The yellow soln was stirred for 1 h in a
60 °C oil bath, and then cooled to r.t. After concentration of the mix-
ture, the residue was subjected to chromatography (silica gel, 5 g,
EtOAc–hexane, 1:4) to give (R)-8a as a white solid; yield: 266.5 mg
(98%); er S/R 0.3:99.7.
1H NMR (CDCl3): δ = 2.39 (s, 3 H, SO2C6H4CH3), 4.64 (d,
J
H,H = 13.06 Hz, 1 H, ArCHHN), 4.73 (d, JH,H = 13.06 Hz, 1 H,
ArCHHN), 5.24 (d, JH,H = 10.31 Hz, 1 H, CH=CHH), 5.41 (d,
JH,H = 17.18 Hz, 1 H, CH=CHH), 5.55 (d, JH,H = 5.73 Hz, 1 H,
ArCHN), 5.89 (ddd,
JH,H = 5.73, 10.31, 17.18 Hz, 1 H,
CHCH=CH2), 7.05–7.08 (m, 1 H, ArH), 7.15–7.18 (m, 1 H, ArH),
7.24 (t, JH,H = 4.12 Hz, 2 H, ArH), 7.28 (d, JH,H = 8.25 Hz, 2 H,
tosyl-ArH), 7.76 (d, JH,H = 8.25 Hz, 2 H, tosyl-ArH).
13C NMR (CDCl3): δ = 21.62, 53.89, 68.65, 116.70, 122.61, 123.58,
127.78, 127.89, 128.26, 129.82, 135.20, 135.45, 138.31, 138.96,
143.66.
[α]D21 –104.9 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.76 (s, 3 H, CH3), 1.77 (s, 3 H, CH3), 3.64
(d, JH,H = 15.84 Hz, 1 H, ArCHHC), 3.74 (d, JH,H = 15.84 Hz, 1 H,
ArCHHC), 4.61 (d, JH,H = 8.94 Hz, 1 H, ArCHC), 5.37 (d,
HRMS (EI): m/z [M+] calcd for C17H17NO2S: 299.0980; found:
299.0978.
JH,H = 9.64 Hz, 1 H, CH=CHH), 5.38 (d, JH,H = 17.21 Hz, 1 H,
CH=CHH), 5.90 (ddd, JH,H = 8.94, 9.64, 17.21 Hz, H,
CHCH=CH2), 7.06 (d, JH,H = 5.51 Hz, 1 H, ArH), 7.21–7.27 (m, 3
H, ArH).
13C NMR (CDCl3): δ = 29.13, 29.83, 43.66, 59.60, 61.80, 105.45,
121.25, 123.96, 124.06, 127.63, 128.13, 134.76, 139.33, 141.27,
167.78, 170.96.
HRMS (ESI): m/z [M + Na+] calcd for C16H16NaO4: 295.0941;
found: 295.0936.
1
2-Tosyl-1-vinyl-1,2,3,4-tetrahydroisoquinoline (8e)
White solid; yield: 368.6 mg (99%); er 99.4:0.6 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H; hexane–i-PrOH, 98:2, 0.8 mL/min
flow rate, 220-nm detection, 27 °C): tR = 33.8, 46.9 min].
[α]D22 –97.0 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 2.36 (s, 3 H, SO2C6H4CH3), 2.62 (ddd,
J
H,H = 5.51, 6.20, 16.04 Hz, 1 H, ArCHHCH2N), 2.72–2.81 (m, 1 H,
ArCHHCH2N), 3.32–3.39 (m, 1 H, ArCH2CHHN), 3.82–3.87 (m, 1
H, ArCH2CHHN), 5.04 (dd, JH,H = 1.15, 17.18 Hz, 1 H, CH=CHH),
5.16 (dd, JH,H = 1.15, 10.31 Hz, 1 H, CH=CHH), 5.55 (d, JH,H = 5.73
Hz, 1 H, ArCHN), 5.90 (ddd, JH,H = 5.73, 10.31, 17.18 Hz, 1 H,
CH=CH2), 7.00 (d, JH,H = 7.45 Hz, 1 H, ArH), 7.06 (d, JH,H = 7.45
Hz, 1 H, ArH), 7.14 (d, JH,H = 6.30, 6.87 Hz, 2 H, ArH), 7.18 (d,
JH,H = 8.02 Hz, 2 H, tosyl-ArH), 7.66 (d, JH,H = 8.02 Hz, 2 H, tosyl-
ArH).
2,2-Dimethyl-1′-(prop-1-en-2-yl)-1′,3′-dihydrospiro[[1,3]diox-
ane-5,2′-indene]-4,6-dione (8b)
White solid; yield: 280.9 mg (98% yield); er 99.5:0.5 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99:1, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 29.6, 44.1 min].
[α]D22 –3.2 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.72 (s, 3 H, CH3), 1.74 (s, 3 H, CH3), 1.81
[s, 3 H, (CH3)C=CH2], 3.67 (s, 2 H, ArCH2C), 4.67 (s, 1 H,
ArCHC), 5.05 (d, JH,H = 1.38 Hz, 1 H, C=CHH), 5.16 (d, JH,H = 1.38
13C NMR (CDCl3): δ = 21.60, 27.82, 39.47, 58.30, 117.75, 126.23,
127.12, 127.32, 1238.06, 129.12, 129.57, 133.69, 133.85, 137.54,
137.92, 143.23.
Synthesis 2012, 44, 2138–2146
© Georg Thieme Verlag Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES
Asymmetric Dehydrative C-, N-, and O-Allylation
2145
HRMS (EI): m/z [M+] calcd for C18H19NO2S: 313.1137; found:
313.1136.
ArCH2CHHO), 5.06 (s, 1 H, CHH=C), 5.09 (s, 1 H, CHH=C), 5.16
(s, 1 H, ArCHO), 7.04 (d, JH,H = 7.57 Hz, 1 H, ArH), 7.11 (d,
J
H,H = 7.57 Hz 1 H, ArH), 7.14–7.19 (m, 2 H, ArH).
2-(tert-Butoxycarbonyl)-1-vinyl-1,2,3,4-tetrahydroisoquinoline
(8f)
Colorless oil; yield: 249.9 mg (96%); 99.8:0.2 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 98:2, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 6.6, 8.8 min].
13C NMR (CDCl3): δ = 17.54, 28.92, 63.72, 81.77, 116.04, 125.79,
126.10, 126.65, 128.83, 134.23, 135.84, 145.41.
HRMS (FAB): m/z [M+] calcd for C12H14O: 174.1045; found:
174.1051.
[α]D20 –118.7 (c 1.0, CHCl3).
8,8-Dimethyl-1-vinyl-7,9-dioxaspiro[4.5]decane-6,10-dione (8j)
White solid; yield: 127.8 mg (57%); er 87.5:12.5 [GC (0.25
mm × 0.12 μm × 30 m Chiraldex B-PM; temp, 100 °C, 140 kPa,
split ratio 100:1): tR = 94.2, 95.7 min]. In this reaction, a 61:39 mix-
ture of (Z)- and (E)-5-(hexa-3,5-dienyl)-2,2-dimethyl-1,3-dioxane-
4,6-dione (30.1 mg, 13% yield) was also isolated.
1H NMR (CDCl3): δ = 1.698 (s, 3 H, CH3), 1.704 (s, 3 H, CH3),
1.98–2.12 (m, 4 H, CH2=CHCHCH2CH2CH2), 2.31–2.42 (m, 2 H,
CH2=CHCHCH2CH2CH2), 3.33 (dt, JH,H = 7.57, 8.26 Hz, 1 H,
CHCH=CH2), 5.13 (dd, JH,H = 1.38, 9.64 Hz, 1 H, CH=CHH), 5.18
(dd, JH,H = 1.38, 17.21 Hz, 1 H, CH=CHH), 5.73 (ddd, JH,H = 8.26,
9.64, 17.21 Hz, 1 H, CHCH=CH2).
1H NMR (CDCl3): δ = 1.48 [s, 9 H, C(CH3)3], 2.71 (dt, JH,H = 4.12,
16.50 Hz, 1 H, ArCHHCH2N), 2.87–2.92 (m, 1 H, ArCHHCH2N),
3.23 (br, 1 H, ArCH2CHHN), 4.06 (br, 1 H, ArCH2CHHN), 5.04
(dd, JH,H = 1.37, 17.18 Hz, 1 H, CH=CHH), 5.13 (dd, JH,H = 1.37,
9.62 Hz, 1 H, CH=CHH), 5.58 (br, 1 H, ArCHN), 5.95 (ddd,
JH,H = 5.50, 9.62, 17.18 Hz, 1 H, CH=CH2), 7.10–7.18 (m, 4 H,
ArH).
13C NMR (CDCl3): δ = 28.63, 28.90, 38.46, 56.99, 79.90, 115.64,
126.15, 126.82, 128.00, 128.94, 135.02, 135.29, 138.09, 154.84.
HRMS (EI): m/z [M + Na+] calcd for C16H21NNaO2: 282.1465;
found: 282.1464.
13C NMR (CDCl3): δ = 25.65, 28.75, 29.81, 32.81, 39.05, 58.43,
100.06, 104.96, 119.08, 135.61, 169.36, 172.21.
HRMS (ESI): m/z [M + Na+] calcd for C12H16NaO4: 247.0941;
found: 247.0940.
1-Vinyl-1,3-dihydroisobenzofuran (8g)
Colorless oil; yield: 129.6 mg (89%); er 99.4:0.6 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H hexane–i-PrOH, 99.7:0.3, 0.8
mL/min flow rate, 220-nm detection, 27 °C): tR = 13.8, 16.2 min].
[α]D20 –67.7 (c 1.09, CHCl3).
1-Tosyl-2-vinylpyrrolidine (8k)
1H NMR (CDCl3): δ = 5.10 (d, JH,H = 12.39 Hz, 1 H, ArCHHO),
5.18 (dd, JH,H = 1.38, 11.71 Hz, 1 H, CH=CHH), 5.25 (d,
White solid; yield: 242.6 mg (97%); er 82.4:17.6 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 98:2, 1.0 mL/min
flow rate, 220-nm detection, 27 °C): tR = 28.4, 31.7 min].
1H NMR (CDCl3): δ = 1.59–1.85 (m, 4 H, NCH2CH2CH2), 2.43 (s,
3 H, SO2C6H4CH3), 3.24 (m, 1 H, NCHH), 3.44 (ddd, JH,H = 4.82,
7.57, 10.16 Hz, 1 H, NCHH), 4.14 (m, 1 H, CHCH=CH2), 5.11 (dd,
J
H,H = 12.39 Hz, 1 H, ArCHHO), 5.43 (dd, JH,H = 1.38, 17.21 Hz, 1
H, CH=CHH), 5.59 (d, JH,H = 7.57 Hz, 1 H, ArCHO), 5.94 (ddd,
H,H = 7.57, 11.71, 17.21 Hz, 1 H, CHCH=CH2), 7.14–7.16 (m, 1 H,
J
ArH), 7.23–7.30 (m, 3 H, ArH).
13C NMR (CDCl3): δ = 73.67, 73.92, 127.02, 127.52, 127.97,
128.81, 130.73, 132.82, 136.14, 139.39.
HRMS (ESI): m/z [M + Na+] calcd for C10H10NaO: 169.0624;
found: 169.0625.
J
H,H = 1.38, 10.33 Hz, 1 H, CH=CHH), 5.27 (dd, JH,H = 1.38, 17.21
Hz, 1 H, CH=CHH), 5.81 (ddd, JH,H = 6.20, 10.33, 17.21 Hz, 1 H,
CHCH=CH2), 7.30 (d, JH,H = 8.26 Hz, 2 H, tosyl-ArH), 7.72 (d,
J
13C NMR (CDCl3): δ = 21.65, 23.88, 32.44, 48.91, 62.04, 115.43,
H,H = 8.26 Hz, 2 H, tosyl-ArH).
127.68, 129.70, 135.36, 138.84, 143.36.
(R)-1-Vinylisochromane [(R)-8h]
Colorless oil; yield: 156.5 mg (98%); er 99.7:0.3 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99.5:0.5, 1.0
mL/min flow rate, 220-nm detection, 27 °C): tR = 8.1 (S), 9.4 min
(R)].
[α]D22 –10.9 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 2.76 (ddd, JH,H = 0.69, 4.13, 15.84 Hz, 1 H,
ArCHHCH2O), 2.94–3.00 (m, 1 H, ArCHHCH2O), 3.86 (ddd,
HRMS (FAB): m/z [M+] calcd for C19H21NO2S: 327.1293; found:
327.1289.
2-Vinyltetrahydrofuran (8l)
According to the reported method,8 the conversion and er were de-
termined by the GC analysis of the reaction mixture; conversion
>99% [GC (J&W Scientific DB-5, 0.25 mm × 0.25 μm × 30 m,
temp, 50 °C for 10 min at >10 °C increase/min to > 200 °C, 140 kPa;
splitless)]; er 60:40 [GC (Chiraldex B-DM, 0.25 mm × 0.25
μm × 30 m, temp 40 °C, 140 kPa; splitless)].
J
J
H,H = 4.13, 8.95, 11.02 Hz, 1 H, ArCH2CHHO), 4.16 (ddd,
H,H = 0.69, 4.82, 11.02 Hz, 1 H, ArCH2CHHO), 5.16 (d,
JH,H = 6.89 Hz, 1 H, ArCHO), 5.34 (d, JH,H = 10.33 Hz, 1 H,
CH=CHH), 5.38 (d, JH,H = 17.21 Hz, 1 H, CH=CHH), 5.97 (ddd,
2,2-Dimethyl-1′-vinyl-1′,3′-dihydrospiro[[1,3]dioxane-5,2′-
indene]-4,6-dione [(R)-8a); Intramolecular Allylation on a
10-Gram Scale
J
H,H = 6.89, 10.33, 17.21 Hz, 1 H, CHCH=CH2), 7.04–7.06 (m, 1 H,
ArH), 7.11–7.13 (m, 1 H, ArH), 7.15–7.19 (m, 2 H, ArH).
A 150-mL Young-type Schlenk tube was charged with [Cp-
Ru(MeCN)3]PF6 (14.9 mg, 34.4 μmol), (S,S)-Naph-diPIM-dioxo-i-
Pr (18.8 mg, 34.4 μmol), and acetone (2.0 mL). The mixture was
stirred at r.t. for 30 min and then the resulting pale yellow soln was
concentrated in vacuo. To this was added CH2Cl2 (35.0 mL), p-
TsOH·H2O (6.5 mg, 34.4 μmol) and 7a (10.0 g, 34.4 mmol). After
stirring at reflux temperature for 3 h followed by cooling to r.t., the
mixture was concentrated and the residue passed through a pad of
silica gel (15 g, 3.5 cm φ × 3.7 cm). The filtrate was concentrated to
give the 5-endo-trig-cyclized product (9.18 g, 98% ); er R/S
99.7:0.3. The white solid was recrystallized [EtOAc (20 mL) and
hexane (60 mL)] to give enantiomerically pure (R)-8a (8.00 g, 85%)
as prismatic crystals; mp 84 °C.
13C NMR (CDCl3): δ = 28.87, 63.29, 78.26, 118.61, 126.10, 126.22,
126.78, 129.04, 133.71, 136.24, 138.18.
HRMS (EI): m/z [M+] calcd for C11H12O: 160.0888; found:
160.0889.
1-(Prop-1-en-2-yl)isochromane (8i)
Colorless oil; yield: 164.5 mg (94%); er 99.1:0.9 [HPLC (5 mm
φ × 250 mm Chiralpak AD-H, hexane–i-PrOH, 99.5:0.5, 1.0
mL/min flow rate, 220-nm detection, 27 °C): tR = 5.4, 6.8 min].
[α]D22 –22.9 (c 1.0, CHCl3).
1H NMR (CDCl3): δ = 1.62 (s, 3 H, CH2=CCH3), 2.69 (ddd,
JH,H = 2.75, 3.44, 15.84 Hz, 1 H, ArCHHCH2O), 3.00–3.08 (m, 1 H,
[α]D20 –108.5 (c 1.0, CHCl3).
ArCHHCH2O), 3.82 (ddd, JH,H = 2.75, 4.13, 11.02 Hz, 1 H,
ArCH2CHHO), 4.18 (ddd, JH,H = 3.44, 5.51, 11.02 Hz, 1 H,
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2138–2146

2146
K. Miyata, M. Kitamura
PRACTICAL SYNTHETIC PROCEDURES
(6) Miyata, K.; Kutsuna, H.; Kawakami, S.; Kitamura, M.
Angew. Chem. Int. Ed. 2011, 50, 4649.
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Synthesis 2012, 44, 2138–2146
© Georg Thieme Verlag Stuttgart · New York