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Abstract: Preformed cationic Rh complexes of the title ligands are effective for the
asymmetric hydroboration/oxidation of vinylarenes at ambient temperature. These
vinylarenes may carry E- or Z-b substituents but not a substituents. Enantiomer
Keywords: asymmetric synthesis
excesses of up to 97 % can be obtained in the most favourable cases. The
catalysts hydroborations ligand
enantioselectivity is moderately sensitive to the structure of the ligand: the
effects rhodium
difurylphosphino ligand gave superior results for electron-poor styrenes and the
diphenylphosphino ligand the best results for electron-rich reactants. Mechanistic
aspects are discussed.
An early key experiment led to the eventual development of Our preliminary experiments[7] indicated that the parent
rhodium-complex-catalysed hydroboration of alkenes.[1] This ligand 1 was a precursor to Rh complexes for the successful
work clearly demonstrated that Wilkinsons catalyst, catalytic hydroboration of simple vinylarenes. For the sim-
[ClRh(PPh3)3], reacts with a cyclic secondary boronate ester plest cases, the reaction proceeded with up to 94 % enantio-
by BH activation and that the h1-borylrhodium hydride selectivity and 99 % regioselectivity in toluene or THF at
releases the reactant on further treatment with Et3SiH. The ambient temperature. A preformed cationic rhodium complex
first examples of this type of catalysis demonstrated the of structure 2 was required; the ligand also forms an air-
potential power of the original experiment, and in particular sensitive, homoleptic 2:1 complex that gives poor enantiose-
the use of catecholborane by Mannig and Nth has been the lectivity under the same conditions. Only vinylarenes give
model on which most further experimentation has been interesting results (in terms of stereoselectivity) and the
based.[2, 3] Burgess and Ohlmeyer were the first to demon- detailed study reported here bears that constraint. Several
strate catalytic asymmetric hydroboration[4] and examples accessible structural variants of the parent ligand 1
permitting high enantiomer excess (ee > 90 %) were devel- (Scheme 1), were used in the investigations. The structures
oped by Hayashis group, which employed rhenium BINAP of the ligand and the reactant were both changed in order to
complexes for the asymmetric hydroboration of simple probe for the relative importance of electronic and steric
styrenes.[5] Subsequently, other catalysts for asymmetric effects. Although ligands 3, 5, 7 and 9 and their respective
hydroboration have been developed; both Togni[6] and rhodium complexes 4, 6, 8 and 10 (as CF3SO 3 or BF 4
Brown[7] employed Rh complexes of heterotopic PN ligands complexes) are all available[10] and a full range of experiments
to give high enantiomer excesses in the hydroboration of is reported; the subsequent discussion will emphasise the
vinylarenes. This field has been reviewed recently.[8] results obtained with the difuranylphosphine complex 8 in
The present paper is concerned with comparisons between comparison with the parent complex 2, as this gave the most
ligands of the type 1,1'-(2-diarylphosphino-1-naphthyl)iso- interesting results. All the catalytic chemistry described here
quinoline ligands[9] involved in Rh-complex-catalysed asym- involves hydroboration followed by peroxide oxidation to
metric hydroboration, and in the effects of the aryl substitu- give the corresponding secondary alcohol. Procedures have
ents on the efficiency and enantiomer excess observed. been published recently for the conversion of the catechol-
boronate ester into a primary amine, whereby the ee is closely
comparable with that obtained in the H2O2 oxidation.[11]
[a] Dr. J. M. Brown, Dr. H. Doucet, Dr. E. Fernandez, Dr. T. P. Layzell
The Dyson Perrins Laboratory
South Parks Rd., Oxford OX1 3QY (England)
Hydroboration of vinylarenes: The initial catalytic experi-
Fax: ( 44) 1865-275674 ments were carried out with freshly distilled catecholborane
E-mail: bjm@ermine.ox.ac.uk in THF, although it was later found that comparable results
1320 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1320 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4
1320 1330
Chem. Eur. J. 1999, 5, No. 4 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1321 $ 17.50+.50/0 1321
FULL PAPER J. M. Brown et al.
Table 2. Hydroboration of electron-poor styrenes. Reaction conditions: tol- Table 3. Hydroboration of vinylarenes. Reaction conditions: toluene, 2 h,
uene, 2 h, ambient temperature, 1 mol % catalyst. ambient temperature, 1 mol % catalyst.
Alkene Catalyst sec-Al- ee[b] Con- Yield Alkene Catalyst sec-Al- ee[b] Con- Yield
cohol[a] figu- cohol[a] figu-
ration ration
1322 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1322 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4
Asymmetric Catalysis 1320 1330
Chem. Eur. J. 1999, 5, No. 4 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1323 $ 17.50+.50/0 1323
FULL PAPER J. M. Brown et al.
1324 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1324 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4
Asymmetric Catalysis 1320 1330
m-CF3 . A plot of log10 (R/S) versus Hammett s gives a present results is that the difurylphosphine-based complex 8 is
modestly reasonable straight line for eleven determinations significantly better with electron-poor vinylarenes; it behaves
(Figure 2), which suggests a simple trend related to the as if it were an electron-rich ligand.
The cone angles of furylphosphines and phenylphosphines
are claimed to be quite similar,[24b] although we caution that
the two ligands possess very different M-P-C-C torsion angles
in their complexes. A comparison of the X-ray structures of
the fragments makes this clear (Figure 3).[24c] In addition, a
superficial analysis of the substituent effects may be mislead-
ing in the assessment of electronic effects, since the relative
contribution of conjugative and inductive effects will depend
on the coordination environment. The definitive attempt by
Joerg and Drago[26] to establish a quantitative basis for
P-donors, based on electrostatic and covalent parameters E
and C, recognises this fact; unfortunately, it does not include
data for trifurylphosphine. Although it is not possible to
define in detail, an electronic effect fits nicely with an
empirical model for the enantioselective hydroboration (vide
infra).
Chem. Eur. J. 1999, 5, No. 4 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1325 $ 17.50+.50/0 1325
FULL PAPER J. M. Brown et al.
planar Pt complexes, electron-rich styrenes coordinate more tural comparison in Figure 3, must be taken into account. This
strongly trans to pyridine than electron-poor analogues;[30] may permit more access to the exo-coordinated alkene and
hence the trend in enantioselectivity seen in Tables 1 and 2 hence an overall diminution of the ee. This explanation
can be explained by a competition between two pathways (see predicts that a bulkier ligand with the electronic properties of
Figure 4): the electronic character of the alkene exerts a the furyl moiety will give superior results. The search is in
progress.
Experimental Section
1326 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1326 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4
Asymmetric Catalysis 1320 1330
stable and were stored in Schlenk tubes under argon. For the catalytic 29 (c 0.5 in chloroform) from catalyst 2 [lit.:[38] [a] 21
D 40.4 (c 0.53
hydroboration reactions the complexes were prepared just before use. in ethanol) reported for the R enantiomer].
[(R)-1-(2-Diphenylphosphino-1-naphthyl)isoquinoline](cyclooctadiene)- 1-(2-Methylphenyl)ethanol: d 7.6 7.1 (m, 4 H), 5.13 (q, 3J(H,H) 6.4 Hz,
rhodium tetrafluoroborate (2): The reaction of [Rh(cod)2]BF4 (41 mg, 1 H), 2.35 (s, 3 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20 D
0.1 mmol) and (R)-1-(2-diphenylphosphino-1-naphthyl)isoquinoline 31.2 (c 0.5 in chloroform) from catalyst 2 [lit.:[36] [a] 16
D 70 (c 0.34 in
(46 mg, 0.105 mmol)[9] gave 66 mg (90 %) complex 2. This complex is not ethanol) reported for the R enantiomer].
air stable and was stored in a Schlenk tube under argon. 1H NMR 1-(2,4-Dimethylphenyl)ethanol: d 7.5 7.0 (m, 3 H), 5.11 (q, 3J(H,H)
(200 MHz, CDCl3): d 8.93 (d, 3J(H,H) 6.3 Hz, 1 H; H3), 8.27 (d, 6.4 Hz, 1 H), 2.32 (s, 6 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.4 Hz, 3 H);
3
J(H,H) 8.5 Hz, 1 H), 8.12 (d, 3J 8.2 Hz, 1 H), 7.97 (d, 3J(H,H) [a] 20
D 51.2 (c 0.5 in chloroform) from catalyst 2 [lit.: [a] 28
D 46.3
[42]
6.5 Hz, 1 H), 7.80 6.70 (m), 5.15 (br s, 2 H; cod), 4.75 (br s, 1 H; cod), 3.98 (c 1.57 in methanol), configuration unassigned but R by analogy with
(br s, 1 H; cod), 3.15 (br s, 1 H; cod), 2.55 (br s, 2 H; cod), 2.15 (br s, 1 H; cod), other results in this paper].
1.85 (br s, 4 H; cod); 31P NMR (101 MHz, CDCl3): d 32.9 (d, J(P,Rh)
142 Hz); MS (APCI ): m/z: 650 [M]. 1-(2,4,6-Trimethylphenyl)ethanol: d 6.80 (s, 2 H), 5.35 (q, 3J(H,H)
6.7 Hz, 1 H), 2.40 (s, 6 H), 2.24 (s, 3 H), 1.70 (br s, 1 H), 1.50 (d, 3J(H,H)
[ (S)-()-1-(2-Di(3-tolyl)phosphino-1-naphthyl)isoquinoline](cycloocta-
D 37.3 (c 0.5 in chloroform) from catalyst 2 [lit.:
6.8 Hz, 3 H); [a] 20 [39]
diene)rhodium tetrafluoroborate (4): The same procedure as for complex 2
[a] 20
D 52.5 (c 1.1 in chloroform) reported for the R enantiomer].
was followed. Yield: 90 %. This complex is not air stable and was stored in a
Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d 8.89 (d, 2-(2,4,6-Trimethylphenyl)ethanol: d 6.84 (s, 2 H), 3.73 (t, 3J(H,H)
3
J(H,H) 6.3 Hz, 1 H; H3), 8.28 (d, 3J(H,H) 7.7 Hz, 1 H), 8.12 (d, 3J 7.5 Hz, 2 H), 2.92 (t, 3J(H,H) 7.5 Hz, 2 H), 2.33 (s, 6 H), 2.28 (s, 3 H), 1.60
7.8 Hz, 1 H), 7.99 (d, 3J(H,H) 6.3 Hz, 1 H), 7.85 6.55 (m), 5.17 (br s, 1 H; (br s, 1 H).
cod), 5.03 (br s, 1 H; cod), 4.77 (br s, 1 H; cod), 3.98 (br s, 1 H; cod), 3.12 (br s, 1-(4-Dimethylaminophenyl)ethanol: d 7.30 (d, 3J(H,H) 8.8 Hz, 2 H),
1 H; cod), 2.70 1.70 (br s, 12 H; cod, 2 Me); 31P NMR (101 MHz, CDCl3): 6.70 (d, 3J(H,H) 8.8 Hz, 2 H), 4.78 (q, 3J(H,H) 6.5 Hz, 1 H), 2.98 (s, 6 H),
d 32.8 (d, J(P,Rh) 140 Hz); MS (APCI ): m/z: 678.5 [M ]. 1.75 (br s, 1 H), 1.51 (d, 3J(H,H) 6.5 Hz, 3 H); [a] 20D 16.4 (c 0.5 in
diene)rhodium tetrafluoroborate (6): The same procedure as for complex 2 for the R enantiomer].
was followed. Yield: 92 %. This complex is not air stable and was stored in a 1-(4-Methoxyphenyl)ethanol: d 7.31 (d, 3J(H,H) 8.6 Hz, 2 H), 6.90 (d,
Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d 8.84 (d, 3
J(H,H) 8.6 Hz, 2 H), 4.87 (t, 3J(H,H) 6.5 Hz, 1 H), 3.82 (s, 3 H), 1.74
3
J(H,H) 6.3 Hz, 1 H; H3), 8.30 (d, 3J(H,H) 7.4 Hz, 1 H), 8.13 (d, 3J (br s, 1 H), 1.48 (d, 3 H), [a] 22D 39.6 (c 0.5 in chloroform, 75 % ee
[41]
)
7.9 Hz, 1 H), 8.01 (d, 3J(H,H) 6.1 Hz, 1 H), 7.90 6.40 (m), 5.15 (br s, 1 H; [lit.:[5] [a] 23
D 45.2 (c 1.01 in chloroform) reported for the R enantiom-
cod), 4.95 (br s, 1 H; cod), 4.82 (br s, 1 H; cod), 4.00 (br s, 1 H; cod), 3.15 (br s, er].
1 H; cod), 2.57 (br s, 2 H; cod), 2.50 1.70 (m, 17 H; cod, 4Me); 31P NMR
1-(4-Ethoxyphenyl)ethanol: d 7.30 (d, 3J(H,H) 8.8 Hz, 2 H), 6.87 (d,
(101 MHz, CDCl3): d 32.1 (d, J(P,Rh) 140 Hz); MS (APCI ): m/z: 3
J(H,H) 8.8 Hz, 2 H), 4.85 (q, 3J(H,H) 6.4 Hz, 1 H), 4.02 (q, 3J(H,H)
706.5 [M].
7.0 Hz, 2 H), 1.80 (br s, 1 H), 1.47 (d, 3J(H,H) 6.4 Hz, 3 H), 1.40 (t,
[ (S )-()-1-(2-Di(2-furyl)phosphino-1-naphthyl)isoquinoline](cycloocta- 3
J(H,H) 8.0 Hz, 3 H); [a] 20
D 46 (c 0.5 in chloroform) from (R)-
diene)rhodium tetrafluoroborate (8): The same procedure as for complex 2 Quinap.
was followed. Yield: 87 %. This complex is not air stable and was stored in a
1-(4-Fluorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 4.86 (q, 3J(H,H) 6.4 Hz,
Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d 8.90 (d,
1 H), 1.90 (br s, 1 H), 1.48 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20
D 24 (c 0.5 in
3
J(H,H) 6.2 Hz, 1 H; H3), 8.23 (m, 2 H), 8.09 (d, 3J 8.1 Hz, 1 H), 8.03
chloroform) from catalyst 2 [lit.:[42] [a] 20
D 40.2 (c 1.2 in chloroform)
5.60 (m), 5.30 (br s, 1 H; cod), 5.15 (br s, 1 H; cod), 4.90 (br s, 2 H; cod), 3.15
reported for the R enantiomer (ee > 97 %)].
(br s, 1 H; cod), 2.60 (br s, 2 H; cod), 2.20 (br s, 1 H; cod), 1.90 1.70 (br s, 4 H;
cod); 31P NMR (101 MHz, CDCl3): d 5.4 (d, J(P,Rh) 147 Hz); MS 1-(3-Fluorophenyl)ethanol: d 7.4 6.8 (m, 4 H), 4.87 (q, 3J(H,H) 6.4 Hz,
(APCI ): m/z: 630.3 [M]. 1 H), 1.90 (br s, 1 H), 1.48 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20
D 16.4 (c 0.5
in chloroform) from catalyst 8 [lit.:[43] [a] 25
D 38.5 (c 1.2 in MeOH)].
[(R)-()-1-(2-Biphenylylenephosphino-1-naphthyl)isoquinoline](cyclooc-
tadiene)rhodium tetrafluoroborate (10): The same procedure as for 1-(2-Fluorophenyl)ethanol: d 7.6 6.8 (m, 4 H), 5.20 (q, 3J(H,H) 6.6 Hz,
complex 2 was followed. Yield: 88 %. This complex is not air stable and 1 H), 2.00 (br s, 1 H), 1.51 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 16.8 (c 0.5
was stored in a Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d in chloroform) from catalyst 8 [lit.:[44] [a] 20
D 45.4 (c 1.4 in CHCl3) for
9.11 (d, 3J(H,H) 6.3 Hz, 1 H; H3), 8.63 (d, 3J(H,H) 6.3 Hz, 1 H), 8.28 (d, the R enantiomer].
3
J 8.6 Hz, 1 H), 8.10 6.60 (m), 5.38 (br s, 2 H; cod), 4.32 (br s, 1 H; cod), 1-(2,6-Difluorophenyl)ethanol: d 7.3 6.6 (m, 4 H), 5.27 (q, 3J(H,H)
4.05 (br s, 1 H; cod), 2.80 1.50 (m, 8 H; cod); 31P NMR (101 MHz, CDCl3): 6.6 Hz, 1 H), 2.10 (br s, 1 H), 1.64 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 5.8
d 29.1 (d, J(P,Rh) 142 Hz); MS (APCI ): m/z: 663.5 [MNH3]. (c 0.5 in chloroform) from catalyst 8.
Catalytic hydroboration with catecolborane. General procedure: A sol- 1-(4-Chlorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 4.85 (q, 3J(H,H) 6.6 Hz,
ution of rhodium complex (4 mmol) in dichloromethane was transferred, 1 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 36 (c 0.5 in
strictly under argon, by means of a cannula to a Schlenk tube. The chloroform) from catalyst 8 [lit.:[45] [a] 20
D 48.8 (c 3.13 in chloroform)
dichloromethane was evaporated in vacuo, then dry toluene (1 mL), olefin reported for the S enantiomer (ee: 99 %)].
(0.4 mmol) and freshly distilled catecholborane (0.45 mmol) were added.
1-(3-Chlorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 4.85 (q, 3J(H,H) 6.6 Hz,
The solution was stirred at 20 8C for 2 h, cooled with an ice bath, and
1 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 32.8 (c 0.5
quenched with ethanol (1 mL). NaOH (1 mL, 2 m in H2O) and H2O2 (1 mL,
in chloroform) from catalyst 8 [lit.:[5] [a] 20
D 36.7 (c 1 in chloroform)
30 % aqueous) were added, the mixture was allowed to warm up to RT over
reported for the R enantiomer (ee: 84.6 %)].
30 min and was then stirred for 2 h at this temperature. Et2O (10 mL) was
added to the mixture, and the organic layer was then washed with 1m 1-(2-Chlorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 5.31 (q, 3J(H,H) 6.6 Hz,
aqueous NaOH solution twice and with water once and then dried over 1 H), 1.80 (br s, 1 H), 1.48 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 21.2 (c 0.5
MgSO4 . After evaporation of the solvent, the product was purified by in chloroform) from catalyst 8 [lit.:[5] [a] 20
D 22.4 (c 1.1 in chloroform)
chromatography on silica (pentane/ether). 1H NMR (200 MHz, CDCl3) reported for the R enantiomer (ee: 72.1 %)].
spectra of the products are shown below: 1-(2,6-Dichlorophenyl)ethanol: d 7.4 7.1 (m, 3 H), 5.58 (dq, 3J(H,H)
1-(4-Methylphenyl)ethanol: d 7.29 (d, 3J(H,H) 8.2 Hz, 2 H), 7.19 (d, 10.4 and 6.9 Hz, 1 H), 3.12 (d, 3J(H,H) 10.4 Hz, 1 H), 1.67 (d, 3J(H,H)
3
J(H,H) 8.2 Hz, 2 H), 4.86 (q, 3J(H,H) 6.6 Hz, 1 H), 2.36 (s, 3 H), 1.80 D 3.4 (c 1 in chloroform) from catalyst 2.
6.9 Hz, 3 H); [a] 20
(br s, 1 H), 1.48 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20 D 50 (c 0.5 in chloro- 1-(4-Trifluoromethylphenyl)ethanol : d 7.7 7.4 (m, 4 H), 4.97 (q,
form) from catalyst 2 [lit.:[5] [a] 20
D 51.6 (c 1 in chloroform) reported for 3
J(H,H) 6.5 Hz, 1 H), 1.80 (br s, 1 H), 1.51 (d, 3J(H,H) 6.5 Hz, 3 H);
the R enantiomer (ee: 93.8 %)]. [a] 20
D 16.4 (c 0.5 in chloroform) and 18.5 (c 0.2 in methanol) from
1-(3-Methylphenyl)ethanol: d 7.4 7.0 (m, 4 H), 4.88 (q, 3J(H,H) 6.4 Hz, catalyst 8 [lit.:[46] [a] 20
D 29.8 (c 1.088 in methanol) reported for the R
1 H), 2.38 (s, 3 H), 1.90 (br s, 1 H), 1.50 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20
D enantiomer (ee: 98.7 %)].
Chem. Eur. J. 1999, 5, No. 4 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1327 $ 17.50+.50/0 1327
FULL PAPER J. M. Brown et al.
1-(3-Trifluoromethylphenyl)ethanol : d 7.7 7.4 (m, 4 H), 4.98 (q, 4-Chromanol: d 7.4 6.7 (m, 4 H), 4.80 (t, 3J(H,H) 3.4 Hz, 1 H), 4.28 (m,
3
J(H,H) 6.4 Hz, 1 H), 1.80 (br s, 1 H), 1.53 (d, 3J(H,H) 6.4 Hz, 3 H); D 44 (c 1 in chloroform) and
2 H), 2.10 (m, 2 H), 1.80 (br s, 1 H); [a] 20
D 21.4 (c 1 in chloroform) from catalyst 8 [lit.:
[a] 20 [47]
[a] 22
D 28 (c 51 (c 1 in ethanol) from catalyst 2 [lit.:[54] [a] 20 D 67 (c 0.5 in
0.78 in methanol) reported for the R enantiomer]. ethanol) reported for the R enantiomer (ee: 98 %)].
1-(2-Trifluoromethylphenyl)ethanol : d 7.9 7.2 (m, 4 H), 5.33 (q, Determination of enantiomeric excesses and absolute configuration
3
J(H,H) 6.4 Hz, 1 H), 2.10 (br s, 1 H), 1.50 (d, 3J(H,H) 6.4 Hz, 3 H); Method A: By NMR with [Eu(hfc)3] as a chiral shift reagent; absolute
D 15.8 (c 0.5 in chloroform) from catalyst 8, [lit.:
[a] 20 [42]
[a] 22
D 29.2 configuration determined by comparison of the sign of optical rotation with
(c 0.795 in methanol) reported for the R enantiomer, 62 % ee]. the literature, unless otherwise stated.
1-[3,5-Bis(trifluoromethyl)phenyl]ethanol: d 7.82 (s, 2 H), 7.70 (s, 1 H), 1-(4-Dimethylaminophenyl)ethanol: ee calculated on CHMe shifted to d
5.03 (q, 3J(H,H) 6.6 Hz, 1 H), 2.10 (br s, 1 H), 1.53 (d, 3J(H,H) 6.6 Hz, 9 10. (S)-() enantiomer was obtained from catalyst 8.
3 H); [a] 20
D 13.2 (c 0.5 in chloroform) from catalyst 8 [lit.:
[48]
[a] 20
D 1-(2-methoxy-1-naphthyl)ethanol: ee calculated on an aromatic proton
21 (c 1, MeOH) reported for the R enantiomer, 94 % ee]. shifted to d 9-10, absolute configuration assumed by analogy.
1-(9-anthryl)ethanol: ee calculated on an aromatic proton shifted to d 9
1-(2-Naphthyl)ethanol: d 7.9 7.6 (m, 5 H), 7.5 7.3 (m, 3 H), 4.95 (q,
10. (R)-() enantiomer was obtained from catalyst (R)-2.
3
J(H,H) 6.8, 1 H), 2.40 (br s, 1 H), 1.50 (d, 3J(H,H) 6.8 Hz, 3 H).
1-ferrocenylethanol: ee calculated on CHMe shifted to d 6 7. (S)-()
1-(1-Naphthyl)ethanol: d 8.12 (d, 3J(H,H) 8.6, 1 H), 7.80 (d, 3J(H,H) enantiomer was obtained from catalyst 8.
8.2, 1 H), 7.78 (d, 3J(H,H) 9.0, 1 H), 7.49 (t, 3J(H,H) 8.3, 1 H), 7.36 (t, 1,2-diphenylethanol: ee calculated on an ortho-aromatic proton shifted to
3
J(H,H) 8.4, 1 H), 7.27 (d, 3J(H,H) 9.0, 1 H), 5.76 (q, 3J(H,H) 6.8, 1 H), d 10 11. (R)-( ) enantiomer was obtained from (R)-Quinap.
2.05 (br s, 1 H), 1.68 (d, 3J(H,H) 6.8 Hz, 3 H); [a] 23 D 23.3 (c 2.0 in 1-acenaphthenol: ee calculated on an aromatic proton shifted to d 9 10.
ethanol) from catalyst 2 [lit.:[42] [a] 28D 66.7 (c 0.31 in methanol) (R)-() enantiomer was obtained from catalyst (R)-2.
reported for the R enantiomer]. 4-chromanol: ee calculated on an aromatic proton shifted to d 10 11.
1-(2-Methoxy-(1)-naphthyl)ethanol: d 8.12 (d, 3J(H,H) 8.6, 1 H), 7.80 The (R)-() enantiomer was obtained from (R)-2.
(d, 3J(H,H) 8.2, 1 H), 7.78 (d, 3J(H,H) 9.0, 1 H), 7.49 (t, 3J(H,H) 8.3, Method B: By gas chromatography with a Chrompack WCOT Fused Silica
1 H), 7.36 (t, 3J(H,H) 8.4, 1 H), 7.27 (d, 3J(H,H) 9.0, 1 H), 5.76 (q, column, CP-Chirasil-DEX CB, 25 m; inlet pressure: 2.90 psi (Table 5).
3
J(H,H) 6.8, 1 H), 3.99 (s, 3 H), 2.05 (br s, 1 H), 1.68 (d, 3J(H,H) 6.8 Hz, Catalytic hydroboration of styrene: Styrene (0.86 mL, 7.5 mmol) was added
3 H); 13C NMR: d 154.5, 129.5, 129.3, 128.8, 126.8, 125.7, 123.8, 122.9, to a solution of catalyst [(S)-2]OTf (0.012 g, 15 mmol, 0.2 mol %) in THF
117.0, 113.5 (Ar) 66.1 (CH), 56.3 (OCH3)), 23.7 ((CH3); MS (APCI): m/z: (5 mL) under argon. The solution was stirred for 5 min and freshly distilled
186 (39 %) 185 (100 %); IR (KBr): n 3307, 1249, 1056 cm1; [a] 22 D 9.45 catecholborane (0.80 mL, 7.5 mmol) was then added. The mixture was
(c 0.92 in chloroform) from catalyst 2. stirred at ambient temperature for 8 h and then quenched with EtOH
1-(9-Anthryl)ethanol: d 8.7 8.5 (m, 2 H), 8.3 (s, 1 H), 8.1 7.8 (m, 2 H), (2 mL). NaOH (2 m, 10 mL) and H2O2 (1 mL) were added and the mixture
7.6 7.3 (m, 4 H), 6.35 (q, 3J(H,H) 6.3, 1 H), 2.10 (br s, 1 H), 1.85 (d, was stirred for 2 h. The reaction mixture was extracted into Et2O, washed
3
J(H,H) 6.3 Hz, 3 H), [a] 22 D 11.47 (c 0.91 in tetrahydrofuran) from (2 m NaOH, H2O, brine) dried over MgSO4 , and the product isolated by
catalyst 2 [lit.:[49] [a] 20
D 15.7 (0.7 in tetrahydrofuran) reported for the R chromatography on Florosil (Et2O/pentane 1:1). This gave (S)-1-phenyl-
enantiomer]. ethanol [0.647 g (71 %, 99 % secondary isomer, 91 % ee by GC as described
2-Furylethanol: d 7.40 (d, 3J(H,H) 1.0 Hz, 1 H), 6.38 (m, 1 H), 6.27 (d, D 50.2 (c 1 in chloroform) [lit:
above)]; [a] 23 [55]
[a] 23
D 54.0 (c 5.1 in
3
J(H,H) 2.7 Hz, 1 H), 4.89 (q, 3J(H,H) 6.6 Hz, 1 H), 1.90 (br s, 1 H), 1.55 chloroform) reported for the (S)-enantiomer].
(d, 3J(H,H) 6.6 Hz, 3 H); [a] 20 D 9.6 (c 0.5 in chloroform) from
Catalytic hydroboration of 1,2-dihydronaphthalene: A solution of catalyst
catalyst 8 [lit.:[50] [a] 20
D 20.8 (c 1.3 in chloroform) reported for the R
[(R)-2]BF4 (8 mmol) in dichloromethane was transferred by means of a
enantiomer (ee: 95 %)]. cannula to a Schlenk tube, strictly under argon. The dichloromethane was
evaporated in a vacuum then dry toluene (10 mL), 1,2-dihydronaphthalene
2-(5-Methylfuryl)ethanol: d 6.11 (d, 3J(H,H) 2.6 Hz, 1 H), 5.91 (d,
(520 mg, 4 mmol) and freshly distilled catecholborane (600 mg, 5 mmol)
3
J(H,H) 2.6 Hz, 1 H), 4.84 (q, 3J(H,H) 6.6 Hz, 1 H), 2.30 (s, 3 H), 1.70
were added. The solution was stirred at 20 8C for 24 h, cooled in an ice bath
(br s, 1 H), 1.53 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20D 8.4 (c 0.5 in chloro-
and quenched with EtOH (5 mL). After the addition of NaOH (5 mL, 2 m
form) from catalyst 8 [lit.:[51] [a] 20
D 8.5 (c 2.2 in chloroform) reported
in H2O) and H2O2 (5 mL., 30 % aqueous), the mixture was allowed to warm
for the R enantiomer (ee: 95 %)].
to RT over 30 min and was then stirred for 2 h at this temperature. Ether
1-Ferrocenylethanol: d 4.53 (q, 3J(H,H) 6.5 Hz, 1 H), 4.3 4.0 (m, 9 H), (20 mL.) was added to the mixture then the aqueous layer was extracted
1.80 (br s, 1 H), 1.45 (d, 3J(H,H) 6.5 Hz, 3 H); [a] 20D 23.6 (c 0.5 in with two portions of dichloromethane (20 mL.) The organic layers were
chloroform) and [a] 20 D 21.4 (c 0.5 in benzene) from catalyst 2 [lit.:
[52]
dried over MgSO4 . After evaporation of the solvents, the product was
[a] 25
D 29.3 (c 1.7 in benzene) reported for the S enantiomer]. purified by chromatography on silica (pentane/ether) to afford 0.564g
1-Phenylpropanol: d 7.5 7.2 (m, 5 H), 4.55 (t, 3J(H,H) 6.7 Hz, 1 H), (95 %) of (R)-1,2,3,4-tetrahydro-1-naphthol (ee: 96.2 % by GC).
2.23 (br s, 1 H), 1.90 1.50 (m, 2 H), 0.88 (d, 3J(H,H) 6.7 Hz, 3 H).
1,2-Diphenylethanol: d 7.4 7.1 (m, 10 H), 4.90 (dd, 3J(H,H) 8.0 and
5.4 Hz, 1 H), 3.2 2.9 (m, 2 H), 1.8 (br s, 1 H); [a] 20
D 34 (c 0.5 in
chloroform) from catalyst 2 [lit.:[53] [a] 20
Acknowledgements
D 8.5 (c 5 in chloroform)
reported for the R enantiomer].
We thank EPSRC, DTI and Chiroscience (Dr. U. Berens), Glaxo Well-
1-(4-Methoxyphenyl)propanol: d 7.28 (d, 3J(H,H) 8.8 Hz, 2 H), 6.90 (d,
come (Dr. A. Payne), Robinson Bros.(Dr. K. Soares), SB (Dr. P. Sheldrake)
3
J(H,H) 8.8 Hz, 2 H), 4.56 (t, 3J(H,H) 6.7 Hz, 1 H), 3.82 (s, 3 H), 1.90
and Zeneca FCMO (Dr. A. J. Blacker) for support under the LINK
1.70 (m, 2 H), 0.91 (t, 3J(H,H) 6.7 Hz, 3 H); [a] 20 D 29 (c 0.5 in
Asymmetric Synthesis Programme. We thank the Spanish Government for
chloroform) and 26.4 (c 0.5 in benzene) from catalyst 2 [lit.:[54] [a] 20
D
a Scholarship (EF). Johnson Matthey kindly provided a loan of RhCl3
36 (c 1 in chloroform) reported for the R enantiomer (ee: 99 %)].
3 H2O.
1-Indanol: d 7.5 7.1 (m, 4 H), 5.19 (t, 3J(H,H) 6.1 Hz, 1 H), 3.2 2.3 (m,
3 H), 2.10 (br s, 1 H), 2.0 1.8 (m, 1 H).
1-Acenaphthenol: d 7.8 7.3 (m, 6 H), 5.72 (dd, 3J(H,H) 7.1 and 2.5 Hz, [1] H. Kono, K. Ito, Y. Nagai, Chemistry Lett. 1976, 1095 1098.
1 H), 3.81 (dd, 2J(H,H) 17.8 and 3J(H,H) 7.1 Hz, 1 H), 3.23 (dd, [2] J. D. Hewes, C. W. Kriemendahl, T. B. Marder, M. F. Hawthorne, J.
2
J(H,H) 17.8 and 3J(H,H) 2.5 Hz, 1 H); [a] 23 D 1.62 (c 1.23 in Am. Chem. Soc. 1984, 106, 5757 5759, and earlier papers in this
chloroform) from (R)-Quinap [lit.:[18] [a]D 1.46 (c 1.23 in chloroform) series.
reported for the R enantiomer]. [3] D. Mannig, H. Noth, Angew. Chem. 1985, 97 979 980; Angew. Chem.
1,2,3,4-Tetrahydro-1-naphthol: d 7.5 7.1 (m, 4 H), 4.80 (t, 3J(H,H) Int. Ed. Engl. 1985, 24, 878 879.
4.3 Hz, 1 H), 3.1 2.7 (m, 2 H), 2.1 1.7 (m, 5 H). [4] K. Burgess, M. J. Ohlmeyer, J. Org. Chem. 1988, 53, 5178 5179.
1328 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1328 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4
Asymmetric Catalysis 1320 1330
[a] Absolute configuration determined by comparison of the sign of optical rotation with the literature. [b] Absolute configuration assigned by similarity in
the order of elution in the GC analysis and from the sign of optical rotation. [c] Absolute configuration assigned by similarity in the order of elution in the GC
analysis. [d] Absolute configuration determined by comparison with an authentic sample (Aldrich). [e] Inlet pressure: 6.7 psi. [f] SGE column; inlet pressure:
14 psi.
[5] T. Hayashi, Y. Matsumoto, Y. Ito, Tetrahedron: Asymmetry 1991, 2, 9350 9393; S. A. Westcott, H. P. Blom, T. B. Marder, R. T. Baker, J.
601 612. Am. Chem. Soc. 1992, 114, 8863 8869.
[6] A. Schnyder, L. Hintermann, A. Togni, Angew. Chem. 1995, 107 996 [20] H. Werner, M. Schafer, O. Nurnberg, J. Wolf, Chem. Ber. 1994, 127,
998; Angew. Chem. Int. Ed. Engl. 1995, 34, 931 933; A. Schnyder, A. 27 38; B. Ebbinghaus, M. T. Madigan, C. E. Osterberg, L. C. Nathan,
Togni, U. Wiesli, Organometallics 1997, 16, 255 260. Acta Crystallogr. C 1988, 44, 21 23; S. D. Chappell, D. J. Cole-
[7] J. M. Brown, D. I. Hulmes, T. P. Layzell, J. Chem. Soc. Chem. Hamilton, A. Galas, M. B. Hursthouse, N. Walker, Polyhedron 1985, 4,
Commun. 1993, 1673 1674; J. M. Valk, G. A. Whitlock, T. P. Layzell, 121 125.
J. M. Brown, Tetrahedron: Asymmetry 1995, 6, 2593 2596. [21] A. E. Dorigo, P. von R. Schleyer, Angew. Chem. 1995, 107 108 111;
[8] I. Beletskaya, A. Pelter, Tetrahedron 1997, 53, 4957 5026; for earlier Angew. Chem. Int. Ed. Engl. 1995, 34, 115 118; D. G. Musaev, K.
work see: K. Burgess, M. J. Ohlmeyer, Chem. Rev. 1991, 91, 1179 1191. Morokuma, J. Phys. Chem. 1996, 100, 6509 6517.
[9] N. W. Alcock, J. M. Brown, D. I. Hulmes, Tetrahedron: Asymmetry [22] Dr. T. P. Layzell, unpublished results; for the ligand synthesis see: J.
1993, 4, 743 756. Sprinz, G. Helmchen, Tetrahedron Lett. 1993, 34, 1769 1772; P.
[10] H. Doucet, J. M. Brown, Tetrahedron: Asymmetry 1997, 8, 3775 3784. von Matt , A. Pfaltz, Angew. Chem. 1993, 105 614 617; Angew. Chem.
[11] E. Fernandez, M. W. Hooper, F. I. Knight, J. M. Brown, Chem. Int. Ed. Engl. 1993, 32, 566 568; G. J. Dawson, C. G. Frost, J.
Commun. 1997, 173 174. Williams, Tetrahedron Lett. 1993, 34, 3149 3150.
[12] F. I. Knight, J. M. Brown, D. Lazzari, A. Ricci, A. J. Blacker, [23] R. D. Topsom, Prog. Phys Org. Chem. 1987, 16, 125 235.
Tetrahedron 1997, 53, 11 411 11 424. [24] a) D. W. Allen, B. F. Taylor, J. Chem. Soc. Dalton Trans. 1982, 51 54;
[13] S. A. Westcott, H. P. Blom, T. B. Marder, R. T. Baker, J. C. Calabrese, b) M. Ogasawara, F. Maseras, N. Gallego-Planas, K. Kawamura, K.
Inorg. Chem. 1993, 32, 2175 2182. Ito, K. Toyota, W. E. Streib, S. Komiya, O. Eisenstein, K. G. Caulton,
[14] J. M. Brown, G. C. Lloyd-Jones, J. Am. Chem. Soc. 1994, 116, 866 Organometallics 1997, 16, 1979 1993; c) X-ray structure of [(fur-
878. yl)3PFe]: C. Santelli-Rouvier, C. Coin, L. Toupet, M. Santelli, J.
[15] W. Huckel, F. Mossner, Liebigs Ann. Chem. 1960, 637, 57 72. Organomet. Chem. 1995, 495, 91 96; X-ray structure of [Ph3PFe]:
[16] J. Jacques, A. Collet, S. H. Wilen, Enantiomers, Racemates and P. E. Riley, R. E. Davis, Inorg. Chem. 1980, 19, 159 165.
Resolutions, Kreiger, Malabar, Florida, 1991. [25] C. Amatore, A. Jutand, G. Meyer, H. Atmani, F. Khalil, F. O. Chahdi,
[17] H. Kwart, D. P. Hoster, J. Org. Chem. 1967, 32, 1867 1870; D. L. Organometallics 1998, 17, 2958 2964.
Garin, D. J. C. Grieco, L. Kelly, J. Org. Chem. 1977, 42, 1249 1251; [26] R. S. Drago, S. Joerg, J. Am. Chem. Soc. 1996, 118, 2654 2663; S.
L. A. Paquette, C. J. Lau, J. Org. Chem. 1987, 52, 1634 1635; M. Joerg, R. S. Drago, J. Sales, Organometallics 1998, 17, 589 599.
Farina, G. Disilvestro, Mol. Cryst. Liq. Cryst. 1988, 161, 177 198. [27] T. Ikariya, Y. Ishii, H. Kawano, T. Arai, M. Saburi, S. Yoshikawa, S.
[18] Y. Hu, H. Ziffre, J. V. Silverton, Can. J. Chem. 1989, 67, 60 62. Akutagawa, J. Chem. Soc. Chem. Commun. 1985, 922 924.
[19] D. A. Evans, G. C. Fu, B. A. Anderson, J. Am. Chem. Soc. 1992, 114, [28] B. P. Cleary, R. Eisenberg, Organometallics 1995, 14, 4525 4534.
6679 6685; K. Burgess, W. A. Van der Donk, S. A. Westcott, T. B. [29] K. Miki, O. Shiotani, Y. Kai, N. Kasai, H. Kanatani, H. Kurosawa,
Marder, R. T. Baker, J. C. Calabrese, J. Am. Chem. Soc. 1992, 114, Organometallics 1983, 2, 585 593; for an overview of metal alkene
Chem. Eur. J. 1999, 5, No. 4 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1329 $ 17.50+.50/0 1329
FULL PAPER J. M. Brown et al.
binding see: J. A. Gladysz, B. J. Boone, Angew. Chem. 1997, 109, 566 [43] K. Naemura, M. Murata, R. Tanaka, M. Yano, K. Hirose, Y. Tobe,
602; Angew. Chem. Int. Ed. Engl. 1997, 36, 551 583. Tetrahedron: Asymmetry, 1996, 7, 3285 3294.
[30] H. Kurosawa, I. Ikeda, J. Organomet. Chem. 1992, 428, 289 301. [44] C. Meier, W. H. G. Laux, Tetrahedron 1996, 52, 589 598.
[31] S. Ogawa, Y. Tajiri, N. Furukawa, Bull. Chem. Soc. Jpn. 1991, 64, [45] Y. Akakabe, M. Takahashi, M. Kamezawa, K. Kikuchi, H. Tachibana,
3182 3184. T. Ohtani, Y. Naoshima, J. Chem. Soc. Perkin Trans. 1995, 1295 1298.
[32] D. G. Allen, G. M. McLaughlin, G. B. Robertson, W. L. Steffen, G. [46] D. J. Mathre, A. S. Thompson, A. W. Douglas, K. Hoogsteen, J. D.
Salem, S. B. Wild, Inorg. Chem. 1982, 21, 1007; H. T. Clarke, H. B. Carrol, E. G. Corley, E. J. J. Grabowski, J. Org. Chem. 1993, 58, 2880
Gillespie, S. Z. Weisshaus, J. Am. Chem. Soc. 1933, 55, 4571 87. 2888.
[33] M. D. Fryzuk, B. Bosnich, J. Am. Chem. Soc. 1977, 99, 6262 6267. [47] K. Naemura, R. Fukada, M. Murata, M. Konishi, K. Hirose, Y. Tobe,
[34] J. M. Brown, P. L. Evans, A. P. James, Organic Syntheses 1989, 68, 64 Tetrahedron: Asymmetry 1995, 6, 2385 2394.
76. [48] S. T. Pickard, H. E. Smith, J. Am. Chem. Soc 1990, 112, 5741 5747.
[35] K. Tani, T. Akutagawa, H. Kumobayashi, T. Taketomi, H. Takaya, A. [49] K. Okada, H. Sakai, M. Oda, A. Yoshimura, T. Ohno, Tetrahedron
Miyashita, R. Noyori, S. Otsuka, J. Am. Chem. Soc. 1984, 106, 5208 Lett. 1989, 30, 1091 1094.
17. [50] M. Kusakabe, Y. Kitano, Y. Koboyashi, F. Sato, J. Org. Chem. 1989, 54,
[36] R. W. Strassburg, R. A. Gregg, C. Walling, J. Am. Chem. Soc. 1947, 69, 2085 2091.
2141 2143. [51] G. Fantin, M. Fogagnolo, A. Medici, P. Pedrini, S. Poli, F. Gardini,
[37] I. V. Andreeva, M. M. Koton, Dokl. Akad. Nauk. SSSR, 1956, 110, Tetrahedron: Asymmetry. 1993, 4, 1607 1612.
75 78. [52] G. W. Gokel, D. Marquarding, I. K. Ugi, J. Org. Chem. 1972, 37, 3052
[38] K. Nakamura, M. Kawasaki, A. Ohno, Bull. Chem. Soc. Japan, 1996, 3058.
69, 1079 1085. [53] W.Gerrard, M. Kenyon, J. Chem. Soc. 1928, 2564 2567.
[39] M. Kasai, C. Froussios, H. Ziffer, J. Org. Chem. 1983, 48, 459 [54] T. Shono, N. Kise, E. Shirakawa, H. Matsumoto, E. Okazaki, J. Org.
464. Chem. 1991, 56, 3063 3067.
[40] S. Hashiguchi, A. Fujii, K. J. Haack, K. Matsumura, T. Ikariya, R. [55] H. L. Holland, T. S. Manoharan, F. Schweizer, Tetrahedron: Asym-
Noyori, Angew. Chem. 1997, 109, 300 303; Angew. Chem. Int. Ed. metry 1991, 2, 335 338.
Engl. 1997, 36, 288 290. [56] J. M. Brown, S. W. Leppard, G. C. Lloyd-Jones, Tetrahedron: Asym-
[41] G. Lloyd-Jones, D. Phil thesis, Oxford, 1992. metry 1992, 3, 261 66.
[42] T. R. Nieduzak, A. L. Margolin, Tetrahedron: Asymmetry 1991, 2,
113 122. Received: September 1, 1998 [F 1384]
1330 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1330 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4