Enantioselective addition of organozinc reagents to aldehydes catalyzed by 3,3′-bis(diphenylphosphinoyl)-BINOL

Article abstract of DOI:10.1002/adsc.200505221

The enantioselective addition of organozinc reagents to aromatic and aliphatic aldehydes 1 gives secondary alcohols 2 with excellent enantioselectivities in high yields through the catalytic use of (R)-3,3′-bis(diphenylphosphinoyl)-BINOL (3) or (R)-3,3′- bis(diphenylthiophosphinoyl)-BINOL (4) without Ti(IV) complexes. The coordination of the O or S atom of a (thio)phosphinoyl group bearing a BINOL backbone to organozinc reagents can efficiently increase the nucleophilicity of the organozinc reagents.

Full text of DOI:10.1002/adsc.200505221

COMMUNICATIONS
DOI: 10.1002/adsc.200505221
Enantioselective Addition of Organozinc Reagents to Aldehydes
Catalyzed by 3,3’-Bis(diphenylphosphinoyl)-BINOL
Manabu Hatano, Takashi Miyamoto, Kazuaki Ishihara*
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan
Fax: (þ81)-52-789-3331/(þ81)-52-789-3222, e-mail: ishihara@cc.nagoya-u.ac.jp
Received: March 3, 2005; Accepted: August 1, 2005
Supporting Information for this article is available on the WWW under http://asc.wiley-vch.de/home/
Abstract: The enantioselective addition of organo-
zinc reagents to aromatic and aliphatic aldehydes 1
gives secondary alcohols 2 with excellent enantio-
selectivities in high yields through the catalytic use
of (R)-3,3’-bis(diphenylphosphinoyl)-BINOL (3)
from the starting BINOL. We report here the highly
enantioselective addition of organozinc to aldehydes
without any other activators, catalyzed by (R)-3,3’-
bis(diphenylphosphinoyl)-BINOL [(R)-3], which can
be derived from (R)-BINOL quantitatively. To the
best of our knowledge, this is the first example of the cat-
alytic asymmetric addition of organozinc reagents to
or
(R)-3,3’-bis(diphenylthiophosphinoyl)-BINOL
(
4) without Ti(IV) complexes. The coordination of
[10]
the O or S atom of a (thio)phosphinoyl group bear-
ing a BINOL backbone to organozinc reagents can
efficiently increase the nucleophilicity of the organo-
zinc reagents.
aldehydes in the presence of phosphine oxide (P¼O)
or phosphine sulfide (P¼S) moieties in chiral O,O li-
gands.
[
11]
(R)-3,3’-Bis(diphenylphosphinoyl)-BINOL [(R)-3]
was prepared almost quantitatively from commercially
[
12]
Keywords: asymmetric catalysis; binaphthol; diethyl-
zinc; enantioselective addition; phosphine oxides;
secondary alcohols
available (R)-BINOL in two steps (Scheme 1). (R)-
BINOL in THF was treated with NaH (2.2 equivs.) fol-
lowed by the dropwise addition of diphenylphosphinic
chloride (2.2 equivs.), to give the corresponding phos-
phinates (R)-5 quantitatively without further purifica-
[
13]
tion. The rearrangement proceeded with LDA (10
equivs.) in THF at À788C to give (R)-3 quantitatively
For carbon-carbon bond-forming reactions, the catalytic as colorless crystals after recrystallization from tol-
[
14]
enantioselective addition to aldehydes of organozinc re- uene/hexane (ca. 1/5). An X-ray analysis of (R)-3 is
agents is a versatile method for synthesizing optically ac- shown in Fig. 1. Hydrogen bonding, which was observed
[
1,2]
tive secondary alcohols.
Chiral zinc and titanium in Naph-O-H···O¼P (1.863 Š) to form a six-membered
complexes can catalyze this reaction through the com- ring, brings us to the assumption that the chelation to Zn
bined use of amino alcohols (N,O ligands), diamines (instead of H) is in this manner, unlike BI-
2
(
N,N ligands), or diols (O,O ligands) as excellent chiral NOLate(k O,O’)-Zn(II) chelation (vide infra). This hy-
[3,4]
auxiliaries. In particular, 1,1’-bi-2-naphthol (BINOL) drogen bonding of (R)-3 was responsible for the ob-
is highly effective in the diethylzinc addition to alde- served downfield shift, such as 10.57 ppm, in the H
1
hydes, although more than a stoichiometric amount of NMR. Moreover, for the synthesis of (R)-3,3’-bis(diphe-
Ti(O-i-Pr) is necessary to achieve both excellent enan- nylthiophosphinoyl)-BINOL [(R)-4] as a new chiral
4
tiomeric excess and chemical yield within a short reac- auxiliary, two consecutive steps were carried out from
[5,6]
[15]
tion time.
The use of a ꢀchiral/achiral activatorꢁ as (R)-3. Reduction of (R)-3 to the corresponding (R)-
an additive to BINOL-Zn(II) catalyst has been effective 3,3’-bis(diphenylphosphanyl)-BINOL [(R)-6] in moder-
for enhancing the catalytic activity without Ti(IV) ate yield was realized by refluxing with trichlorosilane
[7]
complexes. On the other hand, 3,3’-disubstituted BI- (10 equivs.) and N,N-dimethylaniline (40 equivs.) in tol-
[8]
[16]
NOLs have been designed to establish the catalytic uene. Sulfidation of (R)-6 by elemental sulfur (2.2
asymmetric addition of organozinc reagents without equivs.) in refluxing benzene gave (R)-4 in good yield.
[
9]
any other ꢀactivatorsꢁ such as Ti(IV) complexes. How-
First, 10 mol % of (R)-3 bearing a P¼O moiety with a
ever, these efficient 3,3’-functionalized BINOL ana- BINOL skeleton was used to catalyze the addition of di-
logues are sometimes difficult to synthesize in satisfac- ethylzinc (3 equivs.) to aldehydes in THF-toluene (1:1)
tory yields because of the multi-step transformations at room temperature without Ti(O-i-Pr) . These results
4
Adv. Synth. Catal. 2005, 347, 1561 – 1568
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1561

COMMUNICATIONS
Manabu Hatano et al.
Scheme 1. Preparation of (R)-3 and (R)-4.
catalytic asymmetric diethylzinc addition have been lim-
[
17]
ited becausethe reaction is usually performed at room
temperature or lower to establish and/or maintain high
enantioselectivities. In sharp contrast, our catalyst
showed great performance even at 508C probably due
to the rigid chelation of the P¼O moiety to the Zn(II)
center (vide infra), and the catalyst loading could be de-
creased to 5 mol %. Along with a dramatic decrease in
the reaction time, aromatic aldehydes with electron-
withdrawing or-donating groups gave successful results;
for instance, 88% ee and 84% yield within 2 h for 1a,
88% ee and 96% yield within 3 h for 1c, 90% ee and
Figure 1. ORTEP drawing of (R)-3.
92% yield within 0.5 h for 1e, 90% ee and 98% yield
within 1 h for 1f, 90% ee and 98% yield within 0.1 h
for 1h, and 93% ee and 92% yield within 1.5 h for 1k.
Encouraged by the high performance of (R)-3, we ex-
are summarized in Table 1. (R)-3 was shown to be highly
effective for not only aromatic but also aliphatic alde- amined catalytic asymmetric addition to aldehydes with
hydes, and gave the corresponding ethyl adducts with other organozinc reagents such as n-Bu Zn and Ph Zn.
2
2
high enantioselectivities in good to quantitative yields Butylation with aryl aldehydes 1a and 1e was carried
within 24 h. Particularly, aromatic aldehydes with elec- out with 10 mol % of (R)-3 and 3 equivs. of n-Bu Zn
2
tron-donating or -withdrawing groups showed excellent in THF-heptane at room temperature to give the de-
enantioselectivities (up to 97% ee) in almost quantita- sired butyl adducts 7a and 7e; 92% ee and 94% yield
tive yields (entries 1–11). The reactions also proceeded for 7a and 90% ee and 93% yield for 7e, respectively
smoothly for a,b-unsaturated aldehyde (entry 12). For [Eq. (1)]. Enantioselective phenylation to 1 with 1 equiv.
aliphatic aldehydes, in which competitive reduction of- of Ph Zn was also established in the presence of
2
[
18]
ten occurs along with ethylation, the corresponding sec- 10 mol % of Et Zn, and gave the desired phenyl ad-
2
ondary aliphatic alcohols were obtained with high enan- ducts (R)-8 with 81–88% ee in excellent yields (Table 3).
tioselectivities (up to 94% ee) in good yields (entries
1
3–17). (R)-3 could also be used for heterocycles to
give the desired ethyl adducts with 81–92% ee within
h, although low conversion was observed with 3-pyri-
3
dinecarboxaldehyde, and the starting material was re-
covered without side reactions (entries 18–20).
Interestingly, adramatic increase in the catalytic activ-
ity of (R)-3 was observed at 508C without a serious loss
ð1Þ
(R)-4 bearing a P¼S moiety was examined in the di-
of enantioselectivity (Table 2). The heat conditions in ethylzinc addition without Ti(IV) complexes (Table 4).
1562
asc.wiley-vch.de
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2005, 347, 1561 – 1568

Enantioselective Addition of Organozinc Reagents to Aldehydes
COMMUNICATIONS
Table 1. Enantioselective ethylation of aldehydes with (R)-3 at room temperature.
[a]
Entry
Aldehyde (1)
Time [h]
Yield [%]
ee [%]
[
b]
[b]
[b]
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
PhCHO (1a)
3 (12)
18
8
4
1 (24)
3
9
95 (98)
89
95 (96)
89
p-MeOC H CHO (1b)
6
4
p-MeC H CHO (1c)
>99
>99
98 (>99)
93[
6
4
d]
p-PhC H CHO (1d)
93
6
4
[c]
[c]
[c]
[c]
p-ClC H CHO (1e)
94 (96)
94
86
94 (97)
95
6
4
p-FC H CHO (1f)
94
89
6
4
o-FC H CHO (1g)
6
4
[c]
[c]
p-CF C H CHO (1h)
0.5 (4)
>99 (91)
95
3
6
4
3,4-(OCH O)C H CHO (1i)
4
6
4
1
6
2
6
3
1
1
1
1
1
1
1
1
1
1
2
a-NaphCHO (1j)
b-NaphCHO (1k)
PhCꢀCCHO (1l)
82
95
86
73
55
71
72
66
80[
d]
95
[
e]
86[
d]
PhCH CH CHO (1m)
82
91
94
90
93
84
92
81
2
2
c-C H CHO (1n)
12
6
11
n-C H CHO (1o)
12
12
6
3
2
5
11
n-C H CHO (1p)
9
19
n-C H CHO (1q)
1
1
23
2-FurylCHO (1r)
3-ThienylCHO (1s)
3-PyridylCHO (1t)
90
94
30
0.5
[
[
[
[
[
a]
Absolute configuration of 2 is R. The ee values were determined by chiral GC analysis unless otherwise noted.
Temperature was 08C.
Temperature was À208C.
HPLC analysis on OD-H.
HPLC analysis on OJ-H.
b]
c]
d]
e]
High enantioselectivities (83–85% ee) were observed formance of (R)-10 with respect to (R)-3 is probably
for aromatic aldehydes 1a, 1b and 1e, although the cata- not only due to the rigidity of chelation network, but
lytic activity was lower than that of (R)-3 bearing a P¼O also to the fact that the missing second diphenylphosphi-
moiety to give corresponding (R)-2.
noyl moiety induces a competing chelation mode. (R)-
The presence of P¼O in the BINOL structure is criti- BINOL, (R)-BINAP, and (R)-BINAPO were ineffec-
cal (Fig. 2). The lack of P¼O moieties at the 3,3’-posi- tive under our reaction conditions even though they
tions in the C -symmetrical BINOL backbone resulted have the same C -symmetrical binaphthyl structures.
2
2
in failure: lower enantioselectivities and reactivities
We should address the association between the char-
were observed with the use of (R)-6 and (R)-9, which acteristics of the active Zn(II) catalyst and mechanistic
have bulky substituents at the 3,3’-positions but lack aspects. The key to solving these problems should be
the key P¼O units. These results mean that mere bulki- to clarify whether coordination of P¼O (or P¼S) to the
ness at the 3,3’-positions is insufficient to improve the Zn(II) center is present or not (vide supra), and if so to
enantioselectivities. Furthermore, two C -symmetrical isolate the active catalyst or its precursor. Fortunately,
2
P¼O moieties at the 3,3’-positions in the BINOL skele- a single crystal for X-ray analysis was obtained from a
ton are necessary to achieve high catalytic activity, since mixture of (R)-3 and Et Zn (1 equiv. each) in CH Cl -
2
2
2
(
R)-10, which has a diphenylphosphine oxide on only hexane at room temperature for 24 h. The ORTEP
one side was ineffective for this catalysis. The low per- drawings are shown in Fig. 3. The structure of the ob-
Adv. Synth. Catal. 2005, 347, 1561 – 1568
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1563

COMMUNICATIONS
Manabu Hatano et al.
Table 2. Enantioselective ethylation of aldehydes with (R)-3
under heat conditions (508C).
Entry
1
Time [h]
Yield [%]
ee [%]
1
2
3
4
5
6
7
8
9
1a
1b
1c
1d
1e
1f
1h
1i
1k
1m
1r
2
7
3
2
0.5
1
0.1
1
1.5
4
1.5
1.5
84
95
96
98
92
98
98
93
92
50
93
95
88
85
88
85
90
90
90
89
93
86
80
83
1
1
1
0
1
2
1s
Figure 2. Results of ethylation to 1a by chiral binaphthyl li-
gands (10 mol %) at room temperature for 24 h.
Table 3. Enantioselective phenylation of aldehydes with
R)-3.
(
tion, coordinates to four Zn(II) centers. The Zn(II) cen-
ter in the top position coordinates to m -O (1.930 Š) and
4
three P¼O (1.926–1.955 Š) in three different (R)-3
units. Each of the other three Zn(II) centers in bot-
[a]
tom positions coordinates to m -O (1.949–1.966 Š),
Entry
1
Yield [%]
ee [%]
4
Naph–O (1.874–1.887 Š), and O¼PÀC¼CÀO (1.986–
1
2
3
4
5
6
1c
1d
1e
1f
1h
1k
86
93
96
>99
93
85
2
.011 Š and 1.941–1.956 Š, respectively) through che-
82[
2
lation. However, the essential BINOLate(k O,O’) che-
lation to the Zn(II) center did not exist in 11, while we
obtained solid evidence of the coordination of P¼O to
b]
88
[
b]
b]
86[
88
the Zn(II) center. As expected, this Zn(II) cluster (11)
was not an active species; ethylation of 1a proceeded
95
81
[
a]
Absolute configuration of 8 is R. The ee values were deter- with 3.3 mol % of isolated crystal 11 under the same re-
mined by HPLC analysis (OD-H) unless otherwise noted.
action conditions at room temperature for 24 h to give
[
b]
HPLC analysis on OB-H.
31
(
R)-2a in 38% yield and 20% ee. In fact, in a P NMR
study in CD Cl under anhydrous conditions, the addi-
2
2
tion of 1 equiv. of Et Zn to (R)-3 led to a new complex
2
Table 4. Enantioselective ethylation of aldehydes with (R)-4
at room temperature.
(
12) with a singlet peak at 45.84 ppm (major,>98%)
along with 11 as a minor product at 38.75 and 39.40 ppm
<2%) (Fig. 4). Complex 12 was found to be highly
(
moisture sensitive, and gave the inactive catalyst 11 al-
most quantitatively with the partial release of 3 for
Entry
1
Time [h]
Yield [%]
ee [%] 24 h under open-air conditions. This major complex 12
in the NMR study implied a symmetrical structure
1
2
3
1a
1b
1e
8
24
6
85
61
48
83
85
with two P¼O units coordinating to Zn(II) centers, due
to the downfield shift from 38.82 ppm of the free ligand
85
(
R)-3. By analogy to the structure of 11, 12 is assumed to
2
be an oligomeric species without BINOLate(k O,O’)
[
19]
chelation to the Zn(II) center (Fig. 4).
Finally, we turned our attention to the mechanistic as-
noyl)-BINOLate} (m -O)]·(CH Cl ) (11) was self-as- pects of the transition states. Based on the lack of a non-
tained Zn(II) cluster [Zn {(R)-3,3’-bis(diphenyphosphi-
4
3
4
2
2 3
sembled from four Zn(II) metals and three units of linear relationship between the ee of (R)-3 (10 mol %)
R)-3. At the center of this cluster, m -O, which might and the ee of (R)-2a under room temperature condi-
(
4
be derived from adventitious water during recrystalliza- tions, the structure of the Zn(II) complex in our catalysis
1564
asc.wiley-vch.de
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2005, 347, 1561 – 1568

Enantioselective Addition of Organozinc Reagents to Aldehydes
COMMUNICATIONS
Figure 3. ORTEP drawings of self-assembled Zn(II) cluster 11 (hydrogen atoms are omitted for clarity).
is likely to be a monomeric or homochiral oligomeric should dissociate to monomeric species Awith two inde-
species. Although further investigation is necessary to pendent O¼PÀC¼CÀO chelations before forming BI-
2
achieve a full understanding, a catalytic cycle that in- NOLate(k O,O’) chelation, taking advantage of the
[
20]
2
cludes the transition states is proposed in Fig. 4.
postulated non-BINOLate(k O,O’)-Zn(II) structure
[
21]
Particularly with our ligand 3, oligomeric complex 12 by Pu. Eventually, active species B with a C -symmet-
2
Figure 4. Proposed catalytic cycle and transition states for enantioselective diethylzinc addition to aldehydes with (R)-3.
Adv. Synth. Catal. 2005, 347, 1561 – 1568
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1565

COMMUNICATIONS
Manabu Hatano et al.
rical structure should be formed by Et Zn with coordi- (R)-1,1’-Binaphthalene-2,2’-bis(diphenylphosphinate)
2
2
[22]
nation to BINOLate(k O,O’). Coordination of the al- (5)
dehyde to B leads to two possible transition states: TS-1
A solution of (R)-BINOL (2.86 g, 10 mmol) and NaH (ca. 60%
via re-face attack and TS-2 via si-face attack. In these
w/w oil suspension) (0.880 g, 22 mmol) in THF (50 mL) was
stirred for 15 min at 08C under a nitrogen atmosphere. To
this solution was slowly added diphenylphosphinic chloride
transition states, Et Zn at the center position [BINOLa-
2
2
te(k O,O’)-Zn(II)] acts as a reagent in ethylation and
EtZn at both side positions (O¼PÀC¼CÀO) is coordi- (4.19 mL, 22 mmol) at 08C. The mixture was stirred for
nated to an aldehyde in a vacant site and acts as a 15 min at 08C, then warmed to room temperature, and stirred
[11d,11e,11g,22]
Lewis-acid.
Transition state TS-1 is much pref- for 3 h. The resulting mixture was cooled in an ice bath, diluted
with ether (100 mL) and then water (100 mL). The product was
erable to TS-2 for two important reasons, and eventually
leads to (R)-2:1) it avoids not only steric hindrance be-
extracted with ether (30 mLꢁ2) and washed by brine (20 mL).
The combined extracts were dried over MgSO . The organic
4
tween the aldehyde and Et Zn but also the electrical re-
2
phase was concentrated under reduced pressure to give the
crude product [(R)-5] in quantitative yield (6.86 g). This crude
was used to next rearrangement without further purification.
pulsion of lone pairs between P¼O: and C¼O: in the
same direction, and 2) it covers the hydrogen bonding
between formic proton and P¼O to form a five-mem-
[23]
bered ring. Transition state TS-1 can explain the li-
gand effect on enantioselectivity and/or reactivity (3>
(
R)-3,3’-Bis(diphenylphosphinoyl)-BINOL (3)
4
> >10) due to these rigid chelations and the strength
To a solution of i-Pr NH (19.2 mL, 137 mmol) in THF (50 mL)
of the Lewis acidity of the Zn(II) center in side positions.
After carbon-carbon bond-formation, intermediate A is
regenerated.
In summary, we have developed a highly enantioselec-
tive addition of organozinc reagents to aromatic or ali-
phatic aldehydes catalyzed by (R)-3,3’-bis(diphenyl-
phosphinoyl)-BINOL, which could be prepared quanti-
2
was added n-BuLi (86.7 mL of 1.58 M solution in hexane)
at À788C under a nitrogen atmosphere. After 30 min at
À 788C, to this solution was slowly added the THF solution
(
100 mL) of (R)-5 (13.6 mmol, 9.33 g) via cannula. The mixture
was stirred for 3 h at À788C. The resulting mixture was diluted
with ether (50 mL), with brine (50 mL), and with 1 M HCl to
acidify it to ca. pH 1. The product was extracted with ether
tatively in two steps from commercially available (R)- (30 mLꢁ2) and washed by brine (20 mL). The combined ex-
BINOL. The coordination to the Zn(II) center with tracts were dried over MgSO . The organic phase was concen-
4
phosphine oxide (P¼O) in our ligand could promote car- trated under reduced pressure to give the crude product. Re-
crystallization from toluene/hexane (1/5) gave (R)-3 as color-
bon-carbon bond-formation without Ti(O-i-Pr) at
4
less crystals in quantitative yield (9.33 g).
room temperature, or at an unprecedented higher tem-
perature (508C) with a dramatic increase in catalytic ac-
tivity. Studies are now underway to establish the asym-
metric alkynylation and enantioselective addition to ke-
tones and imines.
General Procedure for the Enantioselective
Diethylzinc Addition to Aldehydes (Tables 1 and 2)
A solution of (R)-3 (0.1 mmol) in THF (3 mL) was stirred in a
pyrex Schlenk tube at room temperature for 5 min under a ni-
trogen atmosphere. To the solution was added Et Zn (2.7 mL
2
Experimental Section
of 1.10 M solution in toluene) at À788C. This solution was stir-
red for 30 min, and aldehyde (1) (1 mmol) was added. The re-
sulting mixture was then gradually warmed to room tempera-
ture or 508C, and stirred for 0.1–24 h. After hydrolysis with
General Remarks
All experiments were carried out under an atmosphere of dry
nitrogen. In experiments that required dry solvents, hexane
10 mL of saturated NH Cl aqueous solution, the product was
4
extracted with ether (10 mLꢁ3) and washed by brine
(
dehydrate), benzene (dehydrate), toluene (dehydrate), di-
(10 mL). The combined extracts were dried over MgSO . The
4
chloromethane (dehydrate), and tetrahydrofuran (dehydrate)
organic phase was concentrated under reduced pressure and
the crude product was purified by neutral silica gel column
chromatography (eluent: hexane/EtOAc or pentane/ether),
to give the desired products 2. The enantiomeric purity was de-
termined by GC or HPLC on chiral column.
were purchased from Kanto Chemical Co., Inc. Et Zn (1.10 M
2
in toluene, Aldrich); n-Bu Zn (1.0 M in heptane, Fluka); Ph Zn
2
2
1
31
(
Strem). NMR ( H, P) spectra were measured on a Varian
31
Mercury 300 spectrometer. Chemical shifts of P NMR are ex-
pressed in parts per million downfield from 85% H PO as an
3
4
external standard (d¼0). High performance liquid chromatog-
raphy (HPLC) analysis was conducted using a Shimadzu LC-10
AD coupled diode array-detector SPD-MA-10A-VP and a chi-
ral column of Daicel CHIRALCEL, CHIRALPAK; OD-H,
OJ-H, OB-H. GC analysis was performed with Shimadzu
X-Ray Crystallographic Study
The single crystal was grown from a dichloromethane-hexane
mixed solution at room temperature. The X-ray crystallo-
graphic analysis was performed with a Bruker SMART
APEX diffractometer (graphite monochromator, MoKa radi-
ation, l¼0.71073 Š). The structure was solved by direct meth-
ods and expanded using Fourier techniques.
1
0
7A instruments using CP-cyclodextrin-b-2,3,6-M-19 (i.d.
.25 mmꢁ25 m; CHROMPACK; GL Science Inc.).
Characterization data for compounds 2–8 can be found in
the Supporting Information.
1566
asc.wiley-vch.de
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2005, 347, 1561 – 1568

Enantioselective Addition of Organozinc Reagents to Aldehydes
COMMUNICATIONS
Crystal data for (R)-3,3’-bis(diphenylphosphinoyl)-BINOL
[6] a) F.-Y. Zhang, C.-W. Yip, R. Cao, A. S. C. Chan, Tetra-
hedron: Asymmetry 1997, 8, 585–589; b) F.-Y. Zhang,
A. S. C. Chan, Tetrahedron: Asymmetry 1997, 8, 3651–
[
0
1
(R)-3]: formula C264H O P , colorless, crystal dimensions
192 24 12
3
.20ꢁ0.20ꢁ0.10 mm , monoclinic, space group C2 (#5), a¼
0.709(5) Š, b¼18.515(5) Š, c¼53.426(5) Š, b¼90.282(5)8,
3
655.
[7] a) K. Ding, A. Ishii, K. Mikami, Angew. Chem. Int. Ed.
999, 38, 497–501; b) K. Mikami, M. Terada, T. Korena-
3
À3
V¼10593(6) Š , Z¼2,
1
¼1.292 g cm , m(MoKa)¼
calc
À1
0
.167 mm , T¼173 K. 25528 reflections were independent
1
and unique, and 21519 with I>2s(I) (2q ¼29.318) were
max
ga, Y. Matsumoto, M. Ueki, R. Angeland, Angew. Chem.
Int. Ed. 2000, 39, 3532–3556; c) K. Mikami, R. Ange-
land, K. Ding, A. Ishii, A. Tanaka, N. Sawada, K.
Kudo, M. Senda, Chem. Eur. J. 2001, 7, 730–737;
d) A. M. Costa, C. Jimeno, J. Gavenonis, P. J. Carroll,
P. J. Walsh, J. Am. Chem. Soc. 2002, 124, 6929–6941;
e) K. Ding, H. Du, Y. Yuan, J. Long, Chem. Eur. J.
used for the solution of the structure. The non-hydrogen atoms
were refined anisotropically. R¼0.0555 and Rw¼0.1320. Crys-
tallographic data (excluding structure factors) for the structure
reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication
no. CCDC-262636. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK [Fax: int. codeþ44(1223)336–033; E-mail:
deposit@ccdc.cam.ac.uk].
2
004, 10, 2872–2884.
8] a) K. Maruoka, N. Murase, H. Yamamoto, J. Org. Chem.
993, 58, 2938–2939; b) K. Ishihara, H. Yamamoto, J.
[
[
1
Crystal data for [Zn {(R)-3,3’-bis(Ph P¼O)-BINOLate}
4
2
3
Am. Chem. Soc. 1994, 116, 1561–1562.
(
m -O)]·(CH Cl ) (11): formula C H O P Zn ·C H Cl ,
4 2 2 3 132 90 13 6 4 3 6 6
3
9] a) H. Kitajima, K. Ito, T. Katsuki, Chem. Lett. 1996, 343–
344; b) H. Kitajima, K. Ito, T. Katsuki, Bull. Chem. Soc.
Jpn. 1997, 70, 207–217; c) W.-S. Huang, Q.-S. Hu, L. Pu,
J. Org. Chem. 1998, 63, 1364–1365; d) H. Kodama, J. Ito,
A. Nagaki, T. Ohta, I. Furukawa, Appl. Organometal.
Chem. 2000, 14, 709–714; e) Z.-B. Li, L. Pu, Org. Lett.
yellow, crystal dimensions 0.25ꢁ0.20ꢁ0.15 mm , monoclinic,
space group P2 (#4), a¼15.803(3) Š, b¼22.033(4) Š, c¼
1
3
1
1
9.949(3) Š, b¼103.148(4)8, V¼6763.9(19) Š , Z¼2, 1
¼
calc
À3
À1
.270 g cm , m(MoKa)¼0.946 mm , T¼223 K. 33967 re-
flections were independent and unique, and 22259 with I>
2
s(I) (2qmax ¼29.218) were used for the solution of the struc-
ture. The non-hydrogen atoms were refined anisotropically.
R¼0.0709 and Rw¼0.1812. Crystallographic data (excluding
structure factors) for the structure reported in this paper
have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-
2
004, 6, 1065–1068.
[
[
10] a) Y. Hamasima, D. Sawada, M. Kanai, M. Shibasaki, J.
Am. Chem. Soc. 1999, 121, 2641–2642; b) M. Kanai, Y.
Hamashima, M. Takamura, M. Shibasaki, J. Synth. Org.
Chem. Jpn. 2001, 59, 766–778.
2
61552. Copies of thedata can be obtained free of chargeon ap-
plication to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
11] Precedent examples have been limited to phosphora-
mide [R N P(¼O)] or thiophosphoramide [R N
n
3–n
n
3–n
[
Fax: int. codeþ44(1223)336–033; E-mail: deposit@ccdc.
P(¼S)]; a) K. Soai, Y. Hirose, Y. Ohno, Tetrahedron:
Asymmetry 1993, 4, 1473–1474; b) R. Hulst, H. Heres,
K. Fitzpatrick, N. C. M. W. Peter, R. M. Kellogg, Tetrahe-
dron: Asymmetry 1996, 7, 2755–2760; c) T. Shibata, H.
Tabira, K. Soai, J. Chem. Soc. Perkin Trans. 1 1998,
cam.ac.uk].
Acknowledgements
1
77–178; d) J.-M. Brunel, T. Constantieux, O, Legrand,
Financial support for this project was providedbythe JSPS. KA-
KENHI (15205021) and the 21 Century COE Program “Na-
ture-Guided Materials Processing” of MEXT.
G. Buono, Tetrahedron Lett. 1998, 39, 2961–2964; e) O.
Legrand, J.-M. Brunel, G. Buono, Tetrahedron Lett.
1
st
998, 39, 9419–9422; f) M. Shi, W.-S. Sui, Tetrahedron:
Asymmetry 1999, 10, 3319–3325; g) O. Legrand, J.-M.
Brunel, G. Buono, Tetrahedron Lett. 2000, 41, 2105–
References and Notes
2
109; h) M. Shi, W.-S. Sui, Chirality 2000, 12, 574–580.
[
12] Compound 3 was synthesized via asymmetric oxidative
biaryl coupling with chiral Cu catalyst in 29% and 96%
ee: X. Li, J. Hewgley, C. A. Mulrooney, J. Yang, M. C.
Konzlowski, J. Org. Chem. 2003, 68, 5500–5511.
13] T.-L. Au-Yeung, K.-Y. Chan, R. K. Haynes, I. D. Wil-
liams, L. L. Yeung, Tetrahedron Lett. 2001, 42, 453–456.
14] T.-L. Au-Yeung, K.-Y. Chan, R. K. Haynes, I. D. Wil-
liams, L. L. Yeung, Tetrahedron Lett. 2001, 42, 457–460.
15] H. Takaya, K. Mashima, K. Koyano, M. Yagi, H. Kumo-
bayashi, T. Taketomi, S. Akutagawa, R. Noyori, J. Org.
Chem. 1986, 51, 629–635.
[
1] R. Noyori, M. Kitamura, Angew. Chem. Int. Ed. Engl.
991, 30, 40–69.
2] For reviews, see: a) K. Soai, S. Niwa, Chem. Rev. 1992,
1
[
9
7
2, 833–856; b) L. Pu, H.-B. Yu, Chem. Rev. 2001, 101,
57–824; c) L. Pu, Tetrahedron 2003, 59, 9873–9886.
[
[
[
[
3] a) B. Schmidt, D. Seebach, Angew. Chem. Int. Ed. Engl.
1
991, 30, 99–101; b) B. Schmidt, D. Seebach, Angew.
Chem. Int. Ed. Engl. 1991, 30, 1321–1323; c) D. Seebach,
A. K. Beck, B. Schmidt, Y. M. Wang, Tetrahedron 1994,
5
1
0, 4363–4384; d) B. Weber, D. Seebach, Tetrahedron
994, 50, 7473–7484; e) D. Seebach, A. Pichota, A. K.
[
16] a) D. P. Young, W. E. McEwen, D. C. Velez, J. W. John-
son, C. A. VanderWerf, Tetrahedron Lett. 1964, 5, 359–
Beck, A. B. Pinkerton, T. Litz, J. Karjalainen, V. Gram-
lich, Org. Lett. 1999, 1, 55–58.
3
64; b) C. J. Chapman, C. G. Frost, M. P. Gill-Carey, G.
[
[
4] P. J. Walsh, Acc. Chem. Res. 2003, 36, 739–749.
5] M. Mori, T. Nakai, Tetrahedron Lett. 1997, 38, 6233–
Kociok-Kçhn, M. F. Mahon, A. S. Weller, M. C. Willis,
Tetrahedron: Asymmetry 2003, 14, 705–710.
6
236.
Adv. Synth. Catal. 2005, 347, 1561 – 1568
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1567

COMMUNICATIONS
Manabu Hatano et al.
[
17] a) H. Wally, M. Widhalm, W. Weissensteiner, K. Schlçgl,
Tetrahedron: Asymmetry 1993, 4, 285–288; b) W.-S.
Huang, L. Pu, J. Org. Chem. 1999, 64, 4222–4223.
[19] For 12, a 3:3 Zn(II):(R)-3 complex similar to the struc-
ture reported by Katsuki cannot be ruled out completely.
[9b]
See ref.
[
18] Pioneering work of diphenylzinc transfer: a) C. Bolm, N.
Hermanns, J. P. Hildebrand, K. Mu n˜ iz, Angew. Chem.
Int. Ed. 2000, 39, 3465–3467; b) C. Bolm, M. Kesselgrub-
er, N. Hermanns, J. P. Hildebrand, G. Raabe, Angew.
Chem. Int. Ed. 2001, 40, 1488–1490; c) C. Bolm, J. P. Hil-
debrand, K. Mu n˜ iz, N. Hermanns, Angew. Chem. Int. Ed.
[20] We cannot explain the stereoselectivities by the similar
mechanism with N,N,N’,N’-tetraalkyl-BINOL-3,3’-dicar-
boxamides postulated by Katsuki, because the steric re-
pulsions between aldehyde and phenyl group in the di-
phenylphosphinoyl moiety are not clear in any transition
[9b]
states with our ligand 3. See ref.
2
001, 40, 3284–3308; d) J. Rudolph, T. Rasmussen, C.
Bolm, P.-O. Norrby, Angew. Chem. Int. Ed. 2003, 42,
002–3005.
[21] W.-S. Huang, Q.-S. Hu, L. Pu, J. Org. Chem. 1999, 64,
7940–7956.
[22] W.-S. Huang, L. Pu, Tetrahedron Lett. 2000, 41, 145–149.
3
[
23] E. J. Corey, T. W. Lee, Chem. Commun. 2001, 1321–
329.
1
1568
asc.wiley-vch.de
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2005, 347, 1561 – 1568