Directed branched-regioselective hydroformylation of 2-substituted allylic o-DPPB esters

Article abstract of DOI:10.1002/ejoc.200700120

Branched-regioselective hydroformylation of allylic o-DPPB esters has been accomplished with mono- and disubstituted alkene functions in good to excellent yields and selectivities. Optimized reaction conditions allowed the reaction of even trisubstitued alkenic functions. These reactions occur as a result of a significant rate-accelerating effect exerted by the catalyst-directing o-DPPB group, as exemplified by highly position-, regio-, and diastereoselective hydroformylation of the geranyl and neryl o-DPPB esters. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejoc.200700120

FULL PAPER
DOI: 10.1002/ejoc.200700120
Directed Branched-Regioselective Hydroformylation of 2-Substituted Allylic
o-DPPB Esters[‡]
Bernhard Breit,*[a] Christian U. Grünanger,[a] and Olivier Abillard[a]
Keywords: Homogeneous catalysis / Hydroformylation / C–C coupling / Catalyst-directing group
Branched-regioselective hydroformylation of allylic o-DPPB
esters has been accomplished with mono- and disubstituted
alkene functions in good to excellent yields and selectivities.
Optimized reaction conditions allowed the reaction of even
trisubstitued alkenic functions. These reactions occur as a re-
sult of a significant rate-accelerating effect exerted by the
catalyst-directing o-DPPB group, as exemplified by highly
position-, regio-, and diastereoselective hydroformylation of
the geranyl and neryl o-DPPB esters.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
ters (Scheme 1). Terminal, 1,2-disubstituted, and even tri-
substituted alkene functions react with exceptional levels of
regiocontrol.
Introduction
The hydroformylation of alkenes is one of the most im-
portant applications of homogeneous catalysis in industry,
although its use in laboratory organic synthesis is still
rare.[1,2] Hydrogen and carbon monoxide are added in the
presence of a transition-metal catalyst across the double
bond of an alkene. A new carbon–carbon and carbon–hy-
drogen bond are formed with concomitant introduction of
the aldehyde function, which itself can serve as a versatile
starting point for subsequent skeleton-expanding synthetic
transformations. Today, rhodium catalysts with tailor-made
bidentate ligands allow for a highly linear-selective hydro-
formylation of terminal alkenes.[3] However, branched-re-
gioselective hydroformylation of an alkyl-substituted ter-
minal alkene and position-selective hydroformylation of an
internal unsymmetrical alkene are challenging tasks for
which, to date, no general solution exists.[4]
Scheme 1. Concept of a branched-regioselective hydroformylation
of allylic alcohol derivatives with the aid of a substrate-bound cata-
lyst-directing group (CDG).
Results and Discussion
We recently showed that specific incorporation of sub-
strate-bound catalyst-directing groups into alkenes allows
for high levels of diastereoselective control in the hydrofor-
mylation of allylic, methallylic, and homomethallylic o-
DPPB esters [o-DPPB = ortho-(diphenylphosphanyl)ben-
zoyl].[5] Furthermore, desymmetrizing hydroformylation of
bis(alkenyl)- and bis(allyl)carbinols has been developed em-
ploying the planar chiral ortho-(diphenylphosphanyl)ferro-
cenecarboxylate (o-DPPF) as a directing group.[6]
The o-DPPB function was readily incorporated into a
range of alkenes in good yields upon reaction of the corre-
sponding allylic alcohol with ortho-(diphenylphosphanyl)-
benzoic acid under Steglich esterification conditions[7]
(Table 1).
In a first set of experiments crotyl o-DPPB ester 3 was
subjected to hydroformylation conditions. The catalyst
loading was 0.7 mol-% [Rh(CO)2acac] and the syngas pres-
sure was 40 bar. In order to identify the best solvent in
terms of reaction rate and regioselectivity the reaction tem-
perature was chosen such that the reaction did not reach
complete conversion.
We herein report on the use of the o-DPPB group as an
efficient catalyst-directing group (CDG) allowing for highly
branched-selective hydroformylation of allylic o-DPPB es-
In all cases high regioselectivity in favor of aldehyde 11
was observed. However, a significant effect of the solvent
on reaction rate was noted. Thus, among the solvents inves-
tigated (toluene, THF, Et2O, CH2Cl2) toluene, THF, and
Et2O gave the best reaction rates (Table 2, Entries 1–4). At
room temperature, full conversion was reached with both
[‡] Substrate-Directed Hydroformylation, 7. Part 6: B. Breit, D.
Breuninger, Eur. J. Org. Chem. 2005, 3930–3941.
[a] Institut für Organische Chemie und Biochemie, Albert-Lud-
wigs-Universität Freiburg
Albertstr. 21, 79104 Freiburg, Germany
Fax: +49-761-203-8715
E-mail: bernhard.breit@organik.chemie.uni-freiburg.de
Eur. J. Org. Chem. 2007, 2497–2503
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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B. Breit, C. U. Grünanger, O. Abillard
FULL PAPER
Table 1. Preparation of allylic and homoallylic o-DPPB esters.
0.7 mol-% catalyst loading, 40 bar syngas pressure, and tol-
uene as the reaction solvent at room temperature with an
initial substrate concentration of 0.1 mol/L.
With these optimized conditions in hand, we turned our
attention to the scope and limitations of the substrates.
Thus, o-DPPB esters 1–7 were subjected to these hydrofor-
mylation conditions and the results are depicted in Table 3.
Excellent yield and regioselectivity were achieved for the
parent allylic o-DPPB ester 1.[8] However, hydroformylation
of the homologous homoallylic o-DPPB ester 2 resulted in
a completely region-random reaction. Clearly, during the
selectivity-determining hydrometallation step this system
can efficiently discriminate between eight- and nine-mem-
bered chelate ring formation, but fails to discriminate be-
tween nine- and ten-membered chelate ring formation.
When increasing the steric demand of substituent R in
allylic o-DPPB esters, the regioselectivity decreases (En-
tries 3–6). In the case of styrene derivative 6 it was of inter-
est to learn whether the o-DPPB directing group is capable
of overruling the intrinsic iso-directing effect of the phenyl
substituent. Thus, styrene derivatives usually display regio-
selectivities that favor the iso-aldehyde by more than 90%.
Unfortunately, a mixture of 16 and iso-16 was obtained in-
dicating that the o-DPPB group and the styrene substituent
have opposite directing effects of similar strength. Regiose-
lective hydroformylation can also be accomplished in a
more complex environment, as exemplified with enantio-
merically pure allylic o-DPPB ester 7 (entry 7).
Trisubstituted alkenes are usually tough substrates to hy-
droformylate as the reaction rate of hydroformylation drops
exponentially with the number of substituents at the alkene
function.[2] However, we speculated that the rate-accelerat-
ing effect typical for a directed reaction may allow regiose-
[a] Isolated yield after column chromatography. [b] (E)/(Z) = 70:30.
THF and toluene (Entries 5 and 6). However, toluene was lective hydroformylation of trisubstituted alkene functions
finally chosen as the optimal solvent due to a slightly higher in an allylic position relative to the directing o-DPPB group.
regioselectivity under these conditions. Interestingly, when As a model substrate, prenyl o-DPPB ester 8 was chosen.
increasing the temperature to 30 °C, the regioselectivity de-
Subjecting 8 to the standard optimized reaction condi-
creased. Thus, as optimized reaction conditions we used tions used before gave a conversion after 23.5 h of only 4%
Table 2. Directed-regioselective hydroformylation of crotyl o-DPPB ester 3: Solvent and temperature screening.
Entry[a]
Solvent
T [°C]
Conversion[b] [%]
Yield[c] [%]
Regioselectivity[b] (11/iso-11)
1
2
3
4
5
6
7
toluene
THF
Et2O
CH2Cl2
toluene
THF
10
10
10
10
r.t.
r.t.
30
53
68
52
n.d.
n.d.
n.d.
n.d.
97
97
quant.
97:3
94:6
92:8
95:5
97:3
94:6
92:8
21
quant.
quant.
30
toluene
[a] Initial substrate concentration: c0 = 0.1 . [b] Determined by NMR analysis of the crude reaction mixture. [c] Isolated yield after
column chromatography.
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Eur. J. Org. Chem. 2007, 2497–2503

Hydroformylation of 2-Substituted Allylic o-DPPB Esters
FULL PAPER
Table 3. Directed hydroformylation of allyl and homoallyl o-DPPB tions so far. Finally, in order to achieve complete consump-
esters 1–7 with mono- and disubstituted alkene functions.
tion of the starting material in a reasonable reaction time,
catalyst loading was increased to 1.8 and 2.8 mol-% (En-
tries 7–9). However, only when the initial substrate concen-
tration was simultaneously reduced from 0.1 to 0.03  was
a quantitative conversion of the starting material 8 ob-
served after 48 h with good regioselectivity (Entry 10).
Note that in this particular case the reaction regioselec-
tivity is certainly primarily a result of Keuleman’s rule,
which states that hydroformylation of alkene functions oc-
curs so as to avoid the formation of a quaternary carbon
atom. However, it is likely that the directing effect of the o-
DPPB group is responsible for a significant rate accelera-
tion of the hydroformylation process in the allylic position
in order for hydroformylation of a trisubstituted alkene to
occur under fairly mild conditions. In order to probe this
notion we subjected geranyl and neryl o-DPPB esters 9 and
10 to the reaction conditions optimized for the hydrofor-
mylation of trisubstituted alkene functions [Equation (1)].
If the rate-accelerating effect of the o-DPPB group is signifi-
cant, position-selective hydroformylation of the allylic al-
kene function in the presence of an additional trisubstituted
alkene function should be possible.
(1)
In fact, subjecting 9 and 10 to similar reaction conditions
led to position-selective as well as diastereoselective hydro-
[a] Initial substrate concentration: c0 = 0.1 . [b] Determined by
formylation of the allylic alkene function [Equation (2)].
The diastereoselectivity observed is of course a result of a
stereoelectronically controlled and irreversible syn hydro-
metallation step. Better regioselectivity was noted for the
neryl system with a ratio for 20/iso-19 of 96:4 and an iso-
lated yield of 86%.
NMR analysis of the crude reaction mixture. [c] Isolated yield after
chromatographic workup. [d] c0
1.8 mol-%. [e] dr of 17 = 81:19.
= 0.03 , [Rh(CO)2acac] =
(Table 4, Entry 1). This result indicates the level of difficulty
one encounters when dealing with trisubstituted alkene
functions.
Increasing the reaction temperature to 60 °C gave a much
better conversion (56%) and an excellent regioselectivity in
favor of aldehyde 18. Raising the temperature to 100 °C did
not improve the reaction rate but reduced the regioselectiv-
ity of the reaction (Entry 3). Employing THF as the solvent
did not lead to any improvement either (Entry 4), nor did
employing an increased syngas pressure (Entry 5). Also, ad-
dition of co-ligands, which proved beneficial in an earlier
investigation with respect to reaction rate and selectivity,[5a]
only resulted in a decrease of regioselectivity. Thus, a reac-
tion temperature of 60 °C and a syngas pressure of 40 bar
with toluene as the solvent seemed to offer the best condi-
(2)
Eur. J. Org. Chem. 2007, 2497–2503
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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2499

B. Breit, C. U. Grünanger, O. Abillard
FULL PAPER
Table 4. Directed hydroformylation of allyl o-DPPB ester 8 with a trisubstituted alkene function.
[a]
Entry
Solvent
T [°C]
P [bar]
[Rh] [mol-%]
t [h]
c0 []
Conversion[b] [%]
Regioselectivity[b] (18/iso-18)
1
2
3
4
5
toluene
toluene
toluene
THF
toluene
toluene
toluene
toluene
toluene
toluene
r.t.
60
100
60
70
60
60
60
60
60
40
40
40
40
70
35
40
65
40
40
0.7
0.7
0.7
0.7
0.7
1.8
1.8
1.8
2.8
2.8
23.5
23.5
23.5
23.5
23.5
23.5
23.5
23.5
48
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.03
4
56
51
51
48
78
49
80
93
n.d.
99:1
92:8
99:1
97:3
98:2
94:6
98:2
94:6
96:4
6
7[c]
8
9
10
48
quant.
[a] Initial substrate concentration. [b] Determined by NMR analysis of the crude reaction mixture. [c] With addition of 5.4 mol-% P(OPh)3.
the filtrate, which was then concentrated to dryness. Flash
chromatography with cyclohexane/ethyl acetate (98:2–95:5) pro-
Conclusions
Branched-regioselective hydroformylation of allylic o-
DPPB esters could be accomplished with mono- and disub-
stituted alkene functions in good to excellent yields and
selectivities. Optimized reaction conditions allowed the re-
vided the o-DPPB esters 1–10.
Allyl o-(Diphenylphosphanyl)benzoate (1): o-DPPB ester 1 (655 mg,
96%) was obtained as a colorless solid from allylic alcohol (116 mg,
2.00 mmol), o-DPPBA (643 mg, 2.10 mmol), DMAP (24 mg,
action of even trisubstituted alkenic functions. These reac- 0.20 mmol), and DCC (454 mg, 2.20 mmol). M.p. 87 °C. 1H NMR
(400.1 MHz, CDCl3): δ = 4.68 (ddd, J = 5.8, 1.4, 1.4 Hz, 2 H), 5.21
(ddt, J = 10.4, 1.4, 1.4 Hz, 1 H), 5.32 (ddt, J = 17.2, 1.4, 1.4 Hz, 1
H), 5.88 (ddt, J = 17.2, 10.4, 5.8 Hz, 1 H), 6.95–7.00 (m, 1 H, Ar-
tions occur as a result of a significant rate-accelerating ef-
fect exerted by the catalyst-directing o-DPPB group, as ex-
emplified by highly position- and regioselective hydrofor-
mylation of the geranyl and neryl o-DPPB esters.
H), 7.28–7.46 (m, 12 H, Ar-H), 8.09–8.14 (m, 1 H, Ar-H) ppm. 13
C
NMR (100.6 MHz, CDCl3): δ = 65.9, 118.5, 128.3, 128.5 (2 C),
128.6 (2 C), 128.7 (2 C), 130.8 (d, JC,P = 2.7 Hz), 132.0, 132.1,
134.0 (d, JC,P = 20.8 Hz, 4 C) 134.3 (d, JC,P = 18.8 Hz), 134.4,
137.8 (d, JC,P = 10.1 Hz, 2 C), 140.4 (d, JC,P = 25.6 Hz), 166.5 (d,
JC,P = 2.2 Hz) ppm. 31P NMR (162.0 MHz, CDCl3): δ = –4.4 ppm.
C22H19O2P (346.4): calcd. C 76.29, H 5.49; found C 76.11, H 5.53.
Experimental Section
General Remarks: Reactions were performed in flame-dried glass-
ware under argon (purity Ͼ99.998%). The solvents were dried by
standard procedures, distilled, and stored under argon. All tem-
peratures quoted are uncorrected. 1H and 13C NMR spectra:
Bruker AM-400 or DRX-500 spectrometer with tetramethylsilane
(TMS), chloroform (CHCl3), or benzene (C6H6) as internal stan-
dards. 31P NMR spectra: Varian Mercury 300 spectrometer with
85% H3PO4 as external standard. Melting points: Melting point
apparatus by Dr. Tottoli (Büchi). Elemental analyses: Elementar
Vario EL apparatus. Flash chromatography: silica gel Si 60, E.
Merck AG, Darmstadt, 40–63 µm. Hydroformylation reactions
were performed in 50- and 100-mL stainless-steel autoclaves
equipped with magnetic stirrers. Gases: Carbon monoxide 3.7, hy-
drogen 4.3 (1:1, Messer-Griesheim). The following compounds
were prepared according to literature procedures: (E)-3-Cyclohex-
ylprop-2-en-1-ol,[9] (E)-3-(tert-butyldiphenylsilyl)prop-2-en-1-ol,[10]
(E,S)-3-(2Ј,2Ј-dimethyl-1,3-dioxolan-4Ј-yl)prop-2-en-1-ol,[11] and
ortho-(diphenylphosphanyl)benzoic acid.[12]
Homoallyl o-(Diphenylphosphanyl)benzoate (2): o-DPPB ester 2
(918 mg, 85%) was obtained as a slightly yellow solid from homoal-
lylic alcohol (216 mg, 3.00 mmol), o-DPPBA (964 mg, 3.15 mmol),
DMAP (36 mg, 0.30 mmol), and DCC (681 mg, 3.30 mmol). M.p.
72 °C. 1H NMR (400.1 MHz, CDCl3): δ = 2.37 (dtdd, J = 6.8, 6.8,
1.4, 1.4 Hz, 2 H), 4.24 (d, J = 6.7 Hz, 2 H), 5.06 (ddt, J = 10.3,
1.9, 1.1 Hz, 1 H), 5.10 (dtd, J = 17.1, 1.7, 1.6 Hz, 1 H), 5.77 (ddt,
J = 17.1, 10.3, 6.7 Hz, 1 H), 6.94–6.99 (m, 1 H, Ar-H), 7.27–7.45
(m, 12 H, Ar-H), 8.05–8.10 (m, 1 H, Ar-H) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 33.0, 64.3, 117.2, 128.3, 128.5 (2 C), 128.6
(2 C), 128.7 (2 C), 130.7 (d, JC,P = 2.9 Hz), 132.0, 134.0 (d, JC,P
=
20.5 Hz, 4 C), 134.0, 134.5, 134.7 (d, JC,P = 19.1 Hz), 137.9 (d, JC,P
= 10.4 Hz, 2 C), 140.2 (d, JC,P = 25.4 Hz), 166.8 (d, JC,P = 1.9 Hz)
ppm. 31P NMR (162.0 MHz, CDCl3): δ = –4.7 ppm. C23H21O2P
(360.1): calcd. C 76.65, H 5.87; found C 76.58, H 5.96.
(E)/(Z)-Crotyl o-(Diphenylphosphanyl)benzoate (3): o-DPPB ester 3
(1.72 g, 88%) was obtained as a slightly yellow solid from (E)/(Z)-
General Procedure for the Preparation of o-DPPB Esters 1–10: o-
DPPBA (1.05 equiv.), DMAP (0.1 equiv.), and DCC (1.1 equiv.) crotyl alcohol (389 mg, 5.40 mmol), o-DPPBA (1.73 g, 5.67 mmol),
were successively added to a solution of allylic alcohol (1 equiv.)
in CH2Cl2 (0.3 ) and the resulting mixture was stirred at room
temperature until TLC showed complete consumption of the start-
ing material. Subsequently, the reaction mixture was filtered
through a plug of CH2Cl2-wetted Celite and washed with ad-
ditional CH2Cl2. An appropriate amount of silica gel was added to
DMAP (66 mg, 0.54 mmol), and DCC (1.23 g, 5.94 mmol). M.p.
93 °C. (Z)-3: 1H NMR (400.1 MHz, CDCl3): δ = 1.68 (ddt, J =
7.0, 1.8, 0.9 Hz, 3 H), 4.74 (ddq, J = 6.8, 1.4, 0.9 Hz, 2 H), 5.50–
5.57 (m, 1 H)*, 5.70 (dqt, J = 10.6, 6.7, 1.4 Hz, 1 H), 6.93–6.99
(m, 1 H, Ar-H)*, 7.27–7.45 (m, 12 H, Ar-H)*, 8.06–8.12 (m, 1 H,
Ar-H)* ppm. 13C NMR (100.6 MHz, CDCl3): δ = 13.2, 60.9, 124.1,
2500
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Eur. J. Org. Chem. 2007, 2497–2503

Hydroformylation of 2-Substituted Allylic o-DPPB Esters
FULL PAPER
128.3, 128.5 (2 C), 128.6 (2 C), 128.7 (2 C), 129.5, 130.8 (d, JC,P
2.9 Hz), 131.9, 134.0 (d, JC,P = 20.8 Hz, 4 C), 134.3, 134.6 (d, JC,P
=
3-Methylbut-2-enyl o-(Diphenylphosphanyl)benzoate (8): o-DPPB
ester 8 (1.02 g, 91%) was obtained as a slightly yellow solid from
= 18.8 Hz), 138.0 (d, JC,P = 10.6 Hz, 2 C), 140.3 (d, JC,P = 26.1 Hz), 3-methylbut-2-en-1-ol (258 mg, 3.00 mmol), o-DPPBA (964 mg,
166.9 (d, JC,P = 1.9 Hz) ppm. 31P NMR (162.0 MHz, CDCl3): δ =
3.15 mmol), DMAP (36 mg, 0.30 mmol), and DCC (681 mg,
–4.5 ppm. (E)-3: 1H NMR (400.1 MHz, CDCl3): δ = 1.70 (ddt, J 3.30 mmol). M.p. 58 °C. H NMR (400.1 MHz, CDCl3): δ = 1.67
1
= 6.6, 1.6, 1.2 Hz, 3 H), 4.61 (ddq, J = 6.6, 1.1, 1.1 Hz, 2 H), 5.52
(dtq, J = 15.3, 6.6, 1.6 Hz, 1 H), 5.77 (dqt, J = 15.3, 6.6, 1.2 Hz, 1
(d, J = 1.3 Hz, 3 H), 1.74 (d, J = 1.3 Hz, 3 H), 4.68 (d, J = 7.1 Hz,
2 H), 5.28 (tqq, J = 7.1, 1.3, 1.3 Hz, 1 H), 6.92–6.97 (m, 1 H),
H), 6.93–6.99 (m, 1 H, Ar-H)*, 7.27–7.45 (m, 12 H, Ar-H)*, 8.06– 7.27–7.44 (m, 12 H), 8.06–8.10 (m, 1 H) ppm. 13C NMR
8.12 (m, 1 H, Ar-H)* ppm. 13C NMR (100.6 MHz, CDCl3): δ =
17.8, 60.0, 125.0, 128.3, 128.5 (2 C), 128.6 (2 C), 128.7 (2 C), 130.8
(d, JC,P = 2.9 Hz), 131.4, 131.9, 134.0 (d, JC,P = 20.8 Hz, 4 C),
134.3, 134.6 (d, JC,P = 18.8 Hz), 138.0 (d, JC,P = 10.6 Hz, 2 C),
140.3 (d, JC,P = 26.1 Hz), 166.7 (d, JC,P = 1.9 Hz) ppm. 31P NMR
(162.0 MHz, CDCl3): δ = –4.4 ppm. *Signals overlapping with
those of the other isomer. C23H21O2P (360.4): calcd. C 76.65, H
5.87; found C 76.59, H 6.14.
(100.6 MHz, CDCl3): δ = 18.1, 25.8, 62.2, 118.5, 128.2, 128.4 (2
C), 128.5 (2 C), 128.6 (2 C), 130.7 (d, JC,P = 2.9 Hz), 131.8, 134.0
(d, JC,P = 20.8 Hz, 4 C), 134.3, 134.8 (d, JC,P = 19.3 Hz), 138.1 (d,
JC,P = 11.4 Hz, 2 C), 138.9, 140.3 (d, JC,P = 26.6 Hz), 167.0 (d,
JC,P = 2.2 Hz) ppm. 31P NMR (162.0 MHz, CDCl3): δ = –4.5 ppm.
C24H23O2P (360.1): calcd. C 76.99, H 6.19; found C 76.72, H 6.25.
Geranyl o-(Diphenylphosphanyl)benzoate (9): o-DPPB ester
9
(756 mg, 85%) as a slightly yellow viscous oil from geraniol
(309 mg, 2.00 mmol), o-DPPBA (643 mg, 2.10 mmol), DMAP
(24 mg, 0.20 mmol), and DCC (454 mg, 2.20 mmol). For analytical
data see ref.[13]
(E)-3-Cyclohexylprop-2-enyl o-(Diphenylphosphanyl)benzoate (4): o-
DPPB ester 4 (1.17 g, 91%) was obtained as a slightly yellow vis-
cous oil from (E)-3-cyclohexylprop-2-en-1-ol (420 mg, 3.00 mmol),
o-DPPBA (964 mg, 3.15 mmol), DMAP (36 mg, 0.30 mmol), and
DCC (681 mg, 3.30 mmol). For analytical data see ref.[13]
Neryl o-(Diphenylphosphanyl)benzoate (10): o-DPPB ester 10
(821 mg, 93%) as a slightly yellow viscous oil from nerol (309 mg,
2.00 mmol), o-DPPBA (643 mg, 2.10 mmol), DMAP (24 mg,
0.20 mmol), and DCC (454 mg, 2.20 mmol). For analytical data see
ref.[13]
(E)-3-(tert-Butyldiphenylsilyl)prop-2-enyl o-(Diphenylphosphanyl)-
benzoate (5): o-DPPB ester 5 (307 mg, 97%) was obtained as a
slightly yellow viscous oil from (E)-3-(tert-butyldiphenylsilyl)prop-
2-en-1-ol (160 mg, 0.541 mmol), o-DPPBA (258 mg, 0.930 mmol,
1.70 equiv.), DMAP (11 mg, 0.089 mmol, 0.20 equiv.), and DCC
(202 mg, 0.980 mmol, 1.80 equiv.). 1H NMR (400.1 MHz, CDCl3):
δ = 1.14 (d, J = 1.1 Hz, 9 H), 4.78 (dd, J = 4.8, 1.6 Hz, 2 H), 6.11
(dtd, J = 18.7, 4.8, 1.4 Hz, 1 H), 6.43 (dtd, J = 18.7, 1.5, 1.5 Hz, 1
H), 6.93–7.01 (m, 1 H), 7.20–7.47 (m, 18 H), 7.58–7.63 (m, 4 H),
8.09–8.14 (m, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 18.2,
27.8 (3 C), 67.4, 126.6, 127.7 (4 C), 128.4, 128.5 (2 C), 128.6 (2 C),
128.8 (2 C), 129.3 (2 C), 130.8 (d, JC,P = 2.7 Hz), 132.1 (1 C, Ar-
C), 134.0 (d, JC,P = 20.5 Hz, 4 C), 134.0 (d, JC,P = 20.5 Hz), 134.3,
134.5 (2 C), 136.3 (4 C), 138.0 (d, JC,P = 11.3 Hz, 2 C), 140.6 (d,
JC,P = 27.0 Hz), 144.6, 166.5 (d, JC,P = 2.2 Hz) ppm. 31P NMR
(162.0 MHz, CDCl3): δ = –4.7 ppm. C38H37O2PSi (584.8): calcd. C
78.05, H 6.38; found C 78.31, H 6.12.
General Procedure (GP) 1 for the Hydroformylation of o-DPPB Es-
ters 1–7 (Mono- and Disubstituted Alkene Functions): [Rh(CO)2-
acac] (0.70 mol-%) was added to a solution of the o-DPPB ester
(1 equiv.) in toluene (0.1 ) and the reaction mixture was stirred
until the catalyst had completely dissolved. The resulting solution
was transferred by syringe into an oven-dried stainless-steel tube
autoclave. The argon in the autoclave was removed by a pressuriz-
ing/depressurizing cycle (three times 20 bar H2/CO) and finally the
autoclave was pressurized with 40 bar H2/CO (1:1). The reaction
mixture was stirred at room temperature for 23.5 h. After releasing
the pressure, the solvent was removed in vacuo and CH2Cl2
(30 mL) was added to the reaction mixture. This solution was fil-
tered through silica gel (esters 11–14, 16) or Celite (esters 15, 17),
which was washed with additional CH2Cl2 (30 mL). The solvent of
the filtrate was removed in vacuo, providing aldehydes 11–17 as
slightly yellow highly viscous oils.
(E)-Cinnamyl o-(Diphenylphosphanyl)benzoate (6): o-DPPB ester 6
(1.68 g, 80%) was obtained as a slightly yellow solid from (E)-cin-
namyl alcohol (670 mg, 5.00 mmol), o-DPPBA (1.61 g, 5.25 mmol),
DMAP (60 mg, 0.50 mmol), and DCC (1.14 g, 5.50 mmol). For an-
alytical data see ref.[13]
General Procedure (GP) 2 for the Hydroformylation of o-DPPB Es-
ters 8–10 (Trisubstituted Alkene Functions): [Rh(CO)2acac]
(2.8 mol-%) was added to a solution of the o-DPPB ester (1 equiv.)
in toluene (0.033 ) and the reaction mixture was stirred until the
catalyst had completely dissolved. The resulting solution was trans-
ferred by syringe into an oven-dried stainless-steel tube autoclave.
The argon in the autoclave was removed by a pressurizing/de-
pressurizing cycle (three times 20 bar H2/CO) and finally the auto-
clave was pressurized with 40 bar H2/CO (1:1). The reaction mix-
ture was stirred at 60 °C for 48 h. After releasing the pressure, the
solvent was removed in vacuo and CH2Cl2 (30 mL) was added to
the reaction mixture. This solution was filtered through silica gel,
which was washed with additional CH2Cl2 (30 mL). The solvent of
the filtrate was removed in vacuo, providing aldehydes 8–10 as
slightly yellow highly viscous oils.
(E,S)-3-(2Ј,2Ј-Dimethyl-1,3-dioxolan-4Ј-yl)prop-2-enyl o-(Diphenyl-
phosphanyl)benzoate (7): o-DPPB ester 7 (1.48 g, 88%) was ob-
tained as a slightly yellow viscous oil from (E,S)-3-(2Ј,2Ј-dimethyl-
1,3-dioxolan-4Ј-yl)prop-2-en-1-ol (598 mg, 3.76 mmol), o-DPPBA
(1.21 g, 3.95 mmol), DMAP (45 mg, 0.38 mmol), and DCC
1
(853 mg, 4.14 mmol). H NMR (400.1 MHz, CDCl3): δ = 1.42 (d,
J = 0.6 Hz, 3 H), 1.46 (d, J = 0.6 Hz, 3 H), 3.59 (dd, J = 8.2,
7.6 Hz, 1 H), 4.10 (dd, J = 8.2, 6.2 Hz, 1 H), 4.50 (ddd, J = 7.3,
6.8, 6.4 Hz, 1 H), 4.69 (d, J = 5.7 Hz, 2 H), 5.75 (dddd, J = 15.5,
6.8, 1.0, 1.0 Hz, 1 H), 5.32 (dtd, J = 15.5, 5.7, 0.6 Hz, 1 H), 6.93–
6.98 (m, 1 H), 7.20–7.45 (m, 12 H), 8.07–8.12 (m, 1 H) ppm. 13C
NMR (100.6 MHz, CDCl3): δ = 25.9, 26.7, 64.6, 69.3, 76.2, 109.5,
2-Formylbutyl o-(Diphenylphosphanyl)benzoate (11): According to
GP 1, hydroformylation of 3 (216 mg, 0.600 mmol) was carried out
with [Rh(CO)2acac] (1.1 mg, 4.2 µmol) in toluene (6 mL), giving 11
127.8, 128.3, 128.5 (2 C), 128.6 (2 C), 128.7 (2 C), 130.8 (d, JC,P
2.7 Hz), 131.8, 132.1, 134.0 (d, JC,P = 20.5 Hz, 2 C), 134.0 (d, JC,P
= 20.8 Hz, 2 C), 134.2 (d, JC,P = 19.1 Hz), 134.4, 137.9 (d, JC,P
=
1
=
(227 mg, 97%). H NMR (400.1 MHz, CDCl3): δ = 0.94 (dd, J =
10.9 Hz, 2 C), 140.5 (d, JC,P = 26.8 Hz), 166.4 (d, JC,P = 2.2 Hz) 7.5, 7.5 Hz, 3 H), 1.52 (ddq, J = 14.2, 7.4, 7.3 Hz, 1 H), 1.71 (ddq,
ppm. 31P NMR (162.0 MHz, CDCl3): δ = –4.5 ppm. C27H27O4P
(446.5): calcd. C 72.63, H 6.10; found C 72.72, H 5.93.
J = 14.4, 7.2, 7.1 Hz, 1 H), 2.51 (ddddd, J = 6.9, 6.9, 6.8, 5.0,
2.0 Hz, 1 H), 4.37 (dd, J = 11.4, 5.0 Hz, 1 H), 4.42 (dd, J = 11.5,
Eur. J. Org. Chem. 2007, 2497–2503
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2501

B. Breit, C. U. Grünanger, O. Abillard
FULL PAPER
7.2 Hz, 1 H), 6.89–6.97 (m, 1 H), 7.22–7.42 (m, 12 H), 7.95–8.01
(m, 1 H), 9.60 (d, J = 2.0 Hz, 1 H) ppm. 13C NMR (100.6 MHz,
CDCl3): δ = 11.3, 19.1, 52.3, 62.7, 128.4, 128.6 (2 C), 128.6 (2 C),
3-(tert-Butyldiphenylsilyl)-2-formylpropyl o-(Diphenylphosphanyl)-
benzoate (15): According to GP 1, hydroformylation of 5 (205 mg,
0.351 mmol) was carried out with [Rh(CO)2acac] (0.6 mg, 2 µmol)
in toluene (4 mL), giving 15 (188 mg, 87%). 1H NMR (400.1 MHz,
CDCl3): δ = 1.04 (s, 9 H), 1.19 (dd, J = 15.5, 6.8 Hz, 1 H), 1.60
(dd, J = 15.3, 6.6 Hz, 1 H), 2.60 (ddddd, J = 6.5, 6.5, 6.5, 5.1,
128.8 (2 C), 130.8 (d, JC,P = 2.9 Hz), 132.2, 133.9 (d, JC,P
20.5 Hz, 4 C), 134.0 (d, JC,P = 19.3 Hz), 134.5, 137.9 (d, JC,P
=
=
11.1 Hz), 137.9 (d, JC,P = 11.1 Hz), 140.6 (d, JC,P = 26.8 Hz), 166.6
(d, JC,P = 2.2 Hz), 202.4 ppm. 31P NMR (162.0 MHz, CDCl3): δ = 1.4 Hz, 1 H), 4.08 (dd, J = 11.3, 6.4 Hz, 1 H), 4.11 (dd, J = 11.3,
–4.6 ppm. C24H23O3P (390.1): calcd. C 73.83, H 5.94; found C
73.96, H 5.91.
4.9 Hz, 1 H), 6.88–6.95 (m, 1 H), 7.15–7.45 (m, 18 H), 7.55–7.61
(m, 4 H), 7.90–7.95 (m, 1 H), 9.24 (d, J = 1.5 Hz, 1 H) ppm. 13C
NMR (100.6 MHz, CDCl3): δ = 5.8, 18.3, 27.8 (3 C), 46.8, 64.9,
128.0 (4 C), 128.4, 128.5 (2 C), 128.6 (2 C), 128.7 (d, JC,P = 2.2 Hz,
2 C), 129.7, 129.7, 130.8 (d, JC,P = 2.9 Hz), 132.2, 133.4, 133.6,
133.9 (d, JC,P = 20.8 Hz, 2 C), 133.9 (d, JC,P = 20.8 Hz, 2 C), 134.1
(d, JC,P = 19.6 Hz), 134.5, 136.0 (2 C), 136.1 (2 C), 137.9 (d, JC,P
= 11.3 Hz), 137.9 (d, JC,P = 11.3 Hz), 140.5 (d, JC,P = 27.0 Hz),
166.3 (d, JC,P = 1.9 Hz), 202.0 ppm. 31P NMR (162.0 MHz,
CDCl3): δ = –4.9 ppm. C39H39O3PSi (614.78): calcd. C 76.19, H
6.39; found C 76.48, H 6.39.
2-Formylpropyl o-(Diphenylphosphanyl)benzoate (12): According to
GP 1, hydroformylation of 1 (208 mg, 0.600 mmol) was carried out
with [Rh(CO)2acac] (1.1 mg, 4.2 µmol) in toluene (6 mL), giving 12
1
(226 mg, quant.). H NMR (400.1 MHz, CDCl3): δ = 1.13 (d, J =
7.1 Hz, 3 H), 2.69 (dddq, J = 7.0, 7.0, 5.4, 1.4 Hz, 1 H), 4.37 (dd,
J = 11.3, 5.2 Hz, 1 H), 4.43 (dd, J = 11.2, 6.8 Hz, 1 H), 6.92–6.99
(m, 1 H), 7.16–7.45 (m, 12 H), 7.98–8.06 (m, 1 H), 9.64 (d, J =
1.3 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 10.7, 45.7,
64.4, 128.4, 128.6 (2 C), 128.6 (2 C), 128.8 (2 C), 130.8 (d, JC,P
2.9 Hz), 132.2, 133.9 (d, JC,P = 20.5 Hz, 2 C), 134.0 (d, JC,P
20.8 Hz, 2 C), 134.0 (d, JC,P = 19.3 Hz), 134.5, 137.8 (d, JC,P
=
=
=
2- and 3-Formyl-3-phenylpropyl o-(Diphenylphosphanyl)benzoate
(16): Owing to the reduced reactivity of the starting material 6 in
the hydroformylation reaction the GP 2, featuring a higher catalyst
loading and a lower concentration of the o-DPPB ester, was em-
ployed. Hydroformylation of 6 (205 mg, 0.332 mmol) was carried
out with [Rh(CO)2acac] (1.5 mg, 6.0 µmol, 1.8 mol-%) in toluene
(10 mL, 0.03 ), giving 16 (149 mg, 99%). 2-Formyl-3-phenylpro-
pyl o-(diphenylphosphanyl)benzoate: 1H NMR (400.1 MHz,
CDCl3): δ = 2.76 (dd, J = 13.9, 7.8 Hz, 1 H), 2.90 (ddddd, J = 7.6,
6.2, 6.0, 5.5, 1.5 Hz, 1 H), 3.04 (dd, J = 13.9, 6.4 Hz, 1 H), 4.37–
4.40 (m, 2 H), 6.91–6.97 (m, 1 H)*, 7.09–7.15 (m, 2 H)*, 7.20–7.43
(m, 15 H)*, 7.94–7.99 (m, 1 H)*, 9.67 (d, J = 1.4 Hz, 1 H) ppm.
3-Formyl-3-phenylpropyl o-(diphenylphosphanyl)benzoate: 1H
NMR (400.1 MHz, CDCl3): δ = 1.95 (dddd, J = 14.4, 8.7, 5.7,
5.7 Hz, 1 H), 2.39 (dddd, J = 14.4, 8.2, 6.0, 6.0 Hz, 1 H), 3.55 (dd,
J = 8.7, 6.0 Hz, 1 H), 4.09 (ddd, J = 11.2, 8.1, 5.5 Hz, 1 H), 4.20
(ddd, J = 11.3, 5.8, 5.8 Hz, 1 H), 6.91–6.97 (m, 1 H)*, 7.09–7.15
(m, 2 H)*, 7.20–7.43 (m, 15 H)*, 7.94–7.99 (m, 1 H)*, 9.59 (d, J =
1.1 Hz, 1 H) ppm. *Signals overlapping with those of the other
isomer. 13C NMR (100.6 MHz, CDCl3) of the mixture of regioiso-
mers (doubled signal set): δ = 28.6, 32.0, 52.4, 55.8, 62.6, 62.8,
126.8, 127.9, 128.4, 128.4, 128.5 (2 C), 128.6 (2 C), 128.6 (2 C),
128.6 (2 C), 128.7 (d, JC,P = 4.8 Hz, 2 C), 128.7 (d, JC,P = 4.8 Hz,
2 C), 128.8 (2 C), 129.0 (2 C), 129.1 (2 C), 129.3 (2 C), 130.7 (d,
JC,P = 2.7 Hz), 130.8 (d, JC,P = 2.4 Hz), 132.1, 132.3, 133.9 (d, JC,P
11.1 Hz, 2 C), 140.5 (d, JC,P = 26.8 Hz), 166.6 (d, JC,P = 1.9 Hz),
202.1 ppm. 31P NMR (162.0 MHz, CDCl3):
δ
=
–4.6 ppm.
C23H21O3P (376.4): calcd. C 73.39, H 5.62; found C 73.16, H 5.60.
3- and 4-Formylbutyl o-(Diphenylphosphanyl)benzoate (13): Accord-
ing to GP 1, hydroformylation of 2 (216 mg, 0.600 mmol) was car-
ried out with [Rh(CO)2acac] (1.1 mg, 4.2 µmol) in toluene (6 mL),
giving 13 (208 mg, 89%). Major regioisomer [3-formylbutyl o-(di-
phenylphosphanyl)benzoate, 58%]: 1H NMR (400.1 MHz, CDCl3):
δ = 1.07 (d, J = 7.1 Hz, 3 H), 2.05 (dqd, J = 7.1, 7.0, 6.8 Hz, 1 H),
2.33–2.42 (m, 2 H)*, 4.24 (ddd, J = 6.8, 6.0, 1.9 Hz, 2 H), 6.90–
6.95 (m, 1 H)*, 7.22–7.44 (m, 12 H)*, 8.98–8.06 (m, 1 H)*, 9.56 (d,
J = 1.3 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 13.2,
28.0, 43.4, 62.7, 128.4, 128.5 (2 C), 128.6 (2 C), 128.7 (2 C), 130.7
(d, JC,P = 3.1 Hz), 132.0, 134.0 (d, JC,P = 20.5 Hz, 4 C), 134.5,
134.5 (d, JC,P = 19.5 Hz), 137.9 (d, JC,P = 11.1 Hz, 2 C), 140.2 (d,
JC,P = 26.3 Hz), 167.0 (d, JC,P = 1.9 Hz), 203.9 ppm. 31P NMR
(162.0 MHz, CDCl3): δ = –4.7 ppm. Minor regioisomer [4-for-
mylbutyl o-(diphenylphosphanyl)benzoate, 42%]: 1H NMR
(400.1 MHz, CDCl3): δ = 1.55–1.65 (m, 4 H), 2.33–2.42 (m, 2 H)*,
4.18 (tt, J = 4.0, 2.0 Hz, 2 H), 6.90–6.95 (m, 1 H)*, 7.22–7.44 (m,
12 H)*, 8.98–8.06 (m, 1 H)*, 9.73 (t, J = 1.6 Hz, 1 H) ppm. 13C
NMR (100.6 MHz, CDCl3): δ = 18.7, 29.2, 43.4, 64.7, 128.4, 128.6
(2 C), 128.6 (2 C), 128.8 (2 C), 130.7 (d, JC,P = 2.7 Hz), 132.1,
134.0 (d, JC,P = 20.5 Hz, 4 C), 134.5, 134.7 (d, JC,P = 19.5 Hz),
138.0 (d, JC,P = 10.9 Hz, 2 C), 140.2 (d, JC,P = 26.3 Hz), 167.0 (d,
JC,P = 2.2 Hz), 202.1 ppm. 31P NMR (162.0 MHz, CDCl3): δ =
–4.6 ppm. *Signals overlapping with those of the other isomer.
C24H23O3P (390.4): calcd. C 73.83, H 5.94; found C 73.57, H 5.78.
= 20.8 Hz, 2 C), 133.9 (d, JC,P = 20.8 Hz, 2 C), 134.0 (d, JC,P
20.5 Hz, 2 C), 134.0 (d, JC,P = 20.5 Hz, 2 C), 134.0 (d, JC,P
=
=
19.1 Hz), 134.5, 134.5, 134.6 (d, JC,P = 21.0 Hz), 135.2, 137.7, 137.8
(d, JC,P = 10.9 Hz), 137.8 (d, JC,P = 10.9 Hz), 137.9 (d, JC,P
8.0 Hz), 138.0 (d, JC,P = 7.7 Hz), 140.0 (d, JC,P = 26.6 Hz), 140.6
=
(d, JC,P = 26.8 Hz), 166.5 (d, JC,P = 2.2 Hz), 166.9 (d, JC,P
=
2.2 Hz), 199.6, 201.6 ppm. 31P NMR (162.0 MHz, CDCl3) of the
mixture of regioisomers: δ = –4.6, –4.7 ppm. C29H25O3P (452.5):
calcd. C 76.98, H 5.57; found C 76.72, H 5.64.
3-Cyclohexyl-2-formylpropyl o-(Diphenylphosphanyl)benzoate (14):
According to GP 1, hydroformylation of 4 (241 mg, 0.600 mmol)
was carried out with [Rh(CO)2acac] (1.1 mg, 4.2 µmol) in toluene
1
(6 mL), giving 14 (216 mg, 84%). H NMR (400.1 MHz, CDCl3): (2RS,4S)-3-(2Ј,2Ј-Dimethyl-1Ј,3Ј-dioxolan-4Ј-yl)-2-formylpropyl o-
δ = 0.79–2.06 (m, 13 H), 2.67 (ddddd, J = 7.1, 6.9, 6.9, 5.0, 2.1 Hz,
1 H), 4.33 (dd, J = 11.3, 5.2 Hz, 1 H), 4.36 (dd, J = 11.4, 7.1 Hz,
(Diphenylphosphanyl)benzoate (17) (81:19 Mixture of Dia-
stereomers): According to GP 1, hydroformylation of 7 (268 mg,
1 H), 6.89–6.95 (m, 1 H), 7.22–7.42 (m, 12 H), 7.94–7.99 (m, 1 H), 0.600 mmol) was carried out with [Rh(CO)2acac] (1.1 mg,
9.57 (d, J = 2.4 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ
= 26.1, 26.2, 26.4, 33.3, 33.4, 33.4, 35.0, 48.4, 63.5, 128.4, 128.6 (2
C), 128.6 (2 C), 128.8 (2 C), 130.8 (d, JC,P = 2.7 Hz), 132.2, 134.0
(d, JC,P = 20.5 Hz, 4 C), 134.0 (d, JC,P = 18.6 Hz), 134.5, 137.9 (d,
JC,P = 11.1 Hz), 137.9 (d, JC,P = 10.9 Hz), 140.6 (d, JC,P = 26.8 Hz),
166.6 (d, JC,P = 1.9 Hz), 202.7 ppm. 31P NMR (162.0 MHz,
CDCl3): δ = –4.6 ppm.
4.2 µmol) in toluene (6 mL), giving 17 (269 mg, 94%). 1H NMR
(400.1 MHz, CDCl3): δ = 1.33 (d, J = 0.6 Hz, 3 H), [1.33 (d, J =
0.5 Hz, 3 H)], 1.39 (d, J = 0.5 Hz, 3 H), [1.40 (d, J = 0.5 Hz, 3 H)],
1.66 (ddd, J = 14.2, 9.1, 4.8 Hz, 1 H), 1.98 (ddd, J = 14.2, 8.1,
3.7 Hz, 1 H), 2.80–2.89 (m, 1 H), [3.51 (dd, J = 8.1, 6.8 Hz, 1 H)],
3.52 (dd, J = 8.1, 6.8 Hz, 1 H), [4.04 (dd, J = 8.0, 6.1 Hz, 1 H)],
4.05 (dd, J = 8.1, 6.1 Hz, 1 H), 4.11–4.21 (m, 1 H), 4.48 (dd, J =
2502
www.eurjoc.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 2497–2503

Hydroformylation of 2-Substituted Allylic o-DPPB Esters
FULL PAPER
11.4, 6.3 Hz, 1 H), 4.53 (dd, J = 11.4, 5.2 Hz, 1 H), 6.92–6.99 (m,
2 C), 130.7 (d, JC,P = 2.7 Hz), 132.2, 132.3, 134.0 (d, JC,P = 20.5 Hz,
1 H), 7.15–7.44 (m, 12 H), 7.97–8.03 (m, 1 H), 9.68 (d, J = 1.3 Hz, 4 C), 134.4 (d, JC,P = 32.4 Hz), 134.5, 137.9 (d, JC,P = 8.2 Hz),
1 H), [9.70 (d, J = 1.3 Hz, 1 H)] ppm. 13C NMR (100.6 MHz,
CDCl3): δ = 25.6, 27.0, [30.1], 30.3, 48.2, [48.5], [62.7], 63.5, 69.4,
[69.5], [73.3], 73.5, 109.4, 128.4, 128.6 (2 C), 128.6 (2 C), 128.7 (2
C), 130.8 (d, JC,P = 2.9 Hz), 132.3, 133.6 (d, JC,P = 19.3 Hz), 133.9
(d, JC,P = 20.8 Hz, 4 C), 134.5, 137.8 (d, JC,P = 11.1 Hz, 2 C), 140.6
(d, JC,P = 26.8 Hz), 166.5 (d, JC,P = 1.9 Hz), 201.5 ppm. 31P NMR
(162.0 MHz, CDCl3): δ = –4.7 ppm. The NMR signals in brackets
are the signals of the minor diastereomer if distinguishable from
the signals of the major diastereomer. C28H29O5P (476.5): calcd. C
70.58, H 6.13; found C 70.66, H 5.94.
138.0 (d, JC,P = 8.0 Hz), 140.5 (d, JC,P = 26.6 Hz), 166.7 (d, JC,P =
1.9 Hz), 202.9 ppm. 31P NMR (162.0 MHz, CDCl3): δ = –4.7 ppm.
C30H33O3P (472.6): calcd. C 76.25, H 7.04; found C 76.01, H 6.92.
Acknowledgments
This work was supported by the Fonds der Chemischen Industrie,
the Deutsche Forschungsgemeinschaft (GRK 1038), and the Alf-
ried-Krupp Award for young university teachers. We thank Dr. R.
Krieger and G. Fehrenbach (both Universität Freiburg) for analyti-
cal support.
2-Formyl-3-methylbutyl o-(Diphenylphosphanyl)benzoate (18): Ac-
cording to GP 2, hydroformylation of 8 (224 mg, 0.600 mmol) was
carried out with [Rh(CO)2acac] (4.3 mg, 17 µmol) in toluene
1
(18 mL), giving 18 (184 mg, 76%). H NMR (400.1 MHz, CDCl3):
[1] a) C. D. Frohning, C. W. Kohlpaintner in Applied Homogen-
eous Catalysis with Organometallic Compounds (Eds.: B.
Cornils, W. A. Herrmann), Wiley-VCH, Weinheim, 2000, pp.
29–104; b) K. Weissermel, H.-J. Arpe, Industrial Organic Chem-
istry, Wiley-VCH, Weinheim, 2003, pp. 127–141; c) P. W. N. M.
van Leeuwen, C. Claver (Eds.), Rhodium Catalyzed Hydrofor-
mylation, Kluwer, Dordrecht, 2000.
δ = 0.99 (d, J = 6.8 Hz, 3 H), 1.00 (d, J = 6.8 Hz, 3 H), 2.10 (qqd,
J = 6.8, 6.8, 6.8 Hz, 1 H), 2.44 (dddd, J = 8.5, 6.3, 4.5, 2.5 Hz, 1
H), 4.39 (dd, J = 11.4, 4.5 Hz, 1 H), 4.51 (dd, J = 11.4, 8.4 Hz, 1
H), 6.91–6.97 (m, 1 H), 7.24–7.44 (m, 12 H), 7.96–8.02 (m, 1 H),
9.64 (d, J = 2.5 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ
= 19.9, 20.3, 26.5, 56.7, 61.9, 128.4, 128.6 (2 C), 128.6 (2 C), 128.7
(d, JC,P = 1.5 Hz, 2 C), 130.7 (d, JC,P = 2.7 Hz), 132.2, 133.9 (d,
JC,P = 20.7 Hz, 2 C), 134.0 (d, JC,P = 20.5 Hz, 2 C), 134.0 (d, JC,P
= 19.1 Hz), 134.5, 137.8 (d, JC,P = 7.0 Hz), 137.9 (d, JC,P = 6.8 Hz),
140.5 (d, JC,P = 26.6 Hz), 166.6 (d, JC,P = 1.9 Hz), 202.8 ppm. 31P
NMR (162.0 MHz, CDCl3): δ = –4.7 ppm. C25H25O3P (404.4):
calcd. C 74.24, H 6.23; found C 74.07, H 6.16.
[2] B. Breit, W. Seiche, Synthesis 2001, 1–36.
[3] a) E. Billig, A. G. Abatjoglou, D. R. Bryant (UCC), US Patent
4769498, 1988 [Chem. Abstr. 1989, 111, 117287]; b) T. J. Devon,
G. W. Phillips, T. A. Puckette, J. L. Stavinoha, J. J. Vanderbilt,
US Patent 4694109, 1987 [Chem. Abstr. 1988, 108, 7890]; c)
C. P. Casey, G. T. Whiteker, M. G. Melville, L. M. Petrovich,
J. A. Gavey, D. R. Powell, J. Am. Chem. Soc. 1992, 114, 5535–
5543; d) M. Kranenburg, Y. E. M. van der Burgt, P. C. J.
Kamer, P. W. N. M. van Leeuwen, K. Goubitz, J. Fraanje, Or-
ganometallics 1995, 14, 3081–3089; e) G. D. Cuny, S. L. Buch-
wald, J. Am. Chem. Soc. 1993, 115, 2066–2068.
(2,3-anti)-2-Formyl-3,7-dimethyloct-6-enyl o-(Diphenylphosphanyl)-
benzoate (19): According to GP 2, hydroformylation of 9 (265 mg,
0.600 mmol) was carried out with [Rh(CO)2acac] (4.3 mg, 17 µmol)
in toluene (18 mL), giving 19 (213 mg, 75%). 1H NMR
(400.1 MHz, CDCl3): δ = 0.91 (d, J = 6.9 Hz, 3 H), 1.21–1.48 (m,
3 H), 1.60 (d, J = 0.8 Hz, 3 H), 1.68 (d, J = 1.3 Hz, 3 H), 1.96–
2.08 (m, 2 H), 2.52 (dddd, J = 8.6, 5.1, 4.4, 2.1 Hz, 1 H), 4.35 (dd,
J = 11.4, 4.4 Hz, 1 H), 4.50 (dd, J = 11.4, 8.6 Hz, 1 H), 5.05 (tqq,
J = 7.1, 1.4, 1.4 Hz, 1 H), 6.89–6.97 (m, 1 H), 7.22–7.43 (m, 12 H),
7.94–8.00 (m, 1 H), 9.59 (d, J = 2.0 Hz, 1 H) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 16.4, 17.8, 25.6, 25.8, 30.8, 34.6, 55.2,
62.3, 123.7, 128.4, 128.5 (2 C), 128.6 (2 C), 128.7 (d, JC,P = 3.4 Hz,
2 C), 130.7 (d, JC,P = 2.9 Hz), 132.2, 132.2, 134.0 (d, JC,P = 20.5 Hz,
4 C), 134.3 (d, JC,P = 25.3 Hz), 134.5, 137.9 (d, JC,P = 7.7 Hz),
[4] M. L. Clarke, Curr. Org. Chem. 2005, 9, 701–718.
[5] a) B. Breit, Acc. Chem. Res. 2003, 36, 264–275; B. Breit, P.
Demel, A. Gebert, Chem. Commun. 2004, 114–115; for related
work see: b) I. J. Krauss, C. C.-Y. Wang, J. L. Leighton, J. Am.
Chem. Soc. 2001, 123, 11514–11515; c) R. W. Jackson, P.
Perlmutter, E. E. Tasdelen, J. Chem. Soc., Chem. Commun.
1990, 763–764; d) S. D. Burke, J. E. Cobb, Tetrahedron Lett.
1986, 27, 4237–4240.
[6] B. Breit, D. Breuninger, J. Am. Chem. Soc. 2004, 126, 10244–
10245; B. Breit, D. Breuninger, Eur. J. Org. Chem. 2005, 3916–
3929; B. Breit, D. Breuninger, Eur. J. Org. Chem. 2005, 3930–
3941; B. Breit, D. Breuninger, Synthesis 2005, 2782–2786.
[7] G. Höfle, W. Steglich, H. Vorbrüggen, Angew. Chem. 1978, 90,
602–615; Angew. Chem. Int. Ed. Engl. 1978, 17, 569–583.
[8] Hydroformylation of allylic alcohol with a standard rhodium/
triphenylphosphane catalyst at 70 °C and 10 bar CO/H2 fur-
nishes the linear product in a regioselectivity of 89:11: B. Breit,
W. Seiche, J. Am. Chem. Soc. 2003, 125, 6608–6609.
138.0 (d, JC,P = 7.5 Hz), 140.5 (d, JC,P = 26.6 Hz), 166.7 (d, JC,P
=
1.7 Hz), 202.6 ppm. 31P NMR (162.0 MHz, CDCl3): δ = –4.7 ppm.
C30H33O3P (472.6): calcd. C 76.25, H 7.04; found C 75.89, H 6.98.
(2,3-syn)-2-Formyl-3,7-dimethyloct-6-enyl o-(Diphenylphosphanyl)-
benzoate (20): According to GP 2, hydroformylation of 10 (265 mg,
0.600 mmol) was carried out with [Rh(CO)2acac] (4.3 mg, 17 µmol) [9] D. Goeppel, I. Münster, R. Brückner, Tetrahedron 1994, 50,
in toluene (18 mL), giving 20 (244 mg, 86%). 1H NMR
3687–3708.
[10] G. Auer, M. Oestreich, Chem. Commun. 2006, 311–313.
[11] J. A. Marshall, J. D. Trometer, D. G. Cleary, Tetrahedron 1989,
45, 391–402.
[12] J. E. Hoots, T. B. Rauchfuss, D.-A. Wrobleski, Inorg. Synth.
1982, 21, 175–179.
[13] P. Demel, M. Keller, B. Breit, Chem. Eur. J. 2006, 12, 6669–
6683.
(400.1 MHz, CDCl3): δ = 0.96 (d, J = 6.9 Hz, 3 H), 1.19–1.49 (m,
3 H), 1.59 (d, J = 0.9 Hz, 3 H), 1.67 (d, J = 1.1 Hz, 3 H), 1.90–
1.99 (m, 2 H), 2.54 (dddd, J = 8.7, 5.1, 4.9, 2.3 Hz, 1 H), 4.32 (dd,
J = 11.4, 4.7 Hz, 1 H), 4.52 (dd, J = 11.4, 8.5 Hz, 1 H), 5.05 (tqq,
J = 7.1, 1.4, 1.4 Hz, 1 H), 6.90–6.97 (m, 1 H), 7.22–7.42 (m, 12 H),
7.94–8.00 (m, 1 H), 9.63 (d, J = 2.4 Hz, 1 H) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 17.0, 17.8, 25.6, 25.8, 31.4, 34.1, 55.4,
62.1, 123.7, 128.4, 128.5 (2 C), 128.6 (2 C), 128.7 (d, JC,P = 2.9 Hz,
Received: February 12, 2007
Published Online: March 28, 2007
Eur. J. Org. Chem. 2007, 2497–2503
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2503