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Asymmetric Ligands for Transition-Metal-Catalyzed Reactions 2-Diphenylphosphinobenzoyl Derivatives of C2-Symmetric Diols and Diamines.

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curacy of & 1 u. Optimized cleavage conditions afforded
pure and fully deprotected lipopeptides according to the IS
mass spectra. The IS mass spectra showed the quasi-molecular peaks in high abundance; fragment peaks above 400 u
were not found (Fig. 1 and 2). However, fragments can usually be observed together with solvent signals below 400 u
(data not shown). The degree of fragmentation during IS
ionization is influenced by the applied orifice potential and
is also dependent on the structure of the lipopeptide; in the
ion-spray mass spectrum of a lipopeptide constituting the
synthetic N-terminus of the cytochrome subunit from a bacterial photoreaction center, for example, we observed two
fragment peaks in high abundance, which resulted from
cleavages at proline residues in the peptide chain during ionization." 71
IS-MS proved to be a convenient method for the characterization of lipopeptide vaccines: it is fast and sensitive, and
the sample preparation is very simple. Accuracies of better
than 1 u were achieved routinely for mass determinations
up to 6000. The use of solvent mixtures containing chloroform in IS-MS not only allowed investigation of lipopeptides, but also of other lipophilic compound classes such as
modified cyclodextrins.['81
Asymmetric Ligands for Transition-MetalCatalyzed Reactions: 2-Diphenylphosphinobenzoyl
Derivatives of C,-Symmetric Diols and Diamines**
By Barry M . Trost* and David L. Van Vvanken
The realization of transition-metal-catalyzed asymmetric
hydrogenation". and oxidation". 31 stimulates the search
for chiral ligands for other types of transition-metal-catalyzed reactions. Allylic alkylation catalyzed by palladium
complexes has proved to be particularly recalcitrant in responding to asymmetric induction, since both bond breaking
and bond making occur on the face opposite palladium and
its attendant ligands.f4-'] Of the various scenarios for asymmetric induction in allylic alkylation, differentiating between
prochiral leaving groups as formulated in Equation (a) rep-
Received: July 17, 1991 [Z 4799 IE]
German version: Angew. Chem. 1992, 104, 235
CAS Registry numbers:
Pam,Cys-Ser-Ser-[VP1(135- 154)],
154)], 138128-52-6.
128820-63-3; Pam3Cys-Lys-[VP1(135
-
[l] A. P. Bruins, T. R. Covey, J. D. Henion, Anal. Chem. 1987, 59. 2642.
(21 J. V. Iribarne, B. A. Thomson, J. Chem. Phys. 1976, 64, 2287.
[3] G. Schmelzeisen-Redeker, L. Butfering, F. W. Rollgen, lnt. .IMuss Spectrom. Ion Processes 1989, 90, 139; F. W. Rollgen, E. Bramer-Wegner,
L. Biitfering, .l
Phys. 1987. 48, C6-253.
[4] a) M. Dole, L. L. Mack, R. L. Hines, R. C. Mohley, L. D. Ferguson,
M. B. Alice, J. Chem. Phys. 1968, 49, 2240; h) J. Gieniec, L. L. Mack,
K. Nakamae, C. Gupta, V. Kumar, M. Dole, Biomed. Moss Specfrom.
1984, fl, 259; c) C. M. Whitehouse. R. N. Dreyer, M. Yamashita,
J. B. Fenn, Anal. Chem. 1985, 57, 675.
[5] T. R. Covey, R. F. Bonner, B. 1. Shushan, J. Henion. Rupid Commun.
Moss. Speclrom. 1988, 2, 249.
[6] R. D. Smith, J. A. Loo, C. G. Edmonds, C. J. Baringa, H. R. Udseth,
Anal. Chmz. 1990, 62, 882.
(71 M. Mann, C. K. Meng, J. B. Fenn, A n d . Chem. 1989.61, 1702.
(81 K.-H. Wiesmuller, G. Jung, G. Hess, G. Vaccine 1989, 7 , 29; M. Krug,
G . Folkers, B. Haas, K.-H. Wiesmiiller, S. Freund, G. Jung, Biopolymers
1989, 28, 499; K . Deres, H. Schild, K.-H. Wiesmuller. G. Jung,
H. G. Rammensee, Nrzrwe 1989, 342. 561.
191 K.-H. Wiesmuller, W. Bessler. G. Jung, Hoppe Seyler's Z . Physlol. Chem.
1983,364, 593.
[lo] Ion spray mass spectra were recorded with a triple-quadrupole mass spectrometer API 111 (Sciex, Thornhill, Ontario, Canada) equipped with an
IonSprayT" source. Lipopeptides (ca. 200 pg) were dissolved in chloroform/methanol/lO% aqueous formic acid or 1 % ammonium acetate
(2:3:1, v:v:v; 1 mL), free peptides (ca. 200 pg) in methanol/l% formic
acid (1 : I v:v; 1 mL). The solutions were introduced into the IS source at
a flow rate between 2-10 pLmin- ' using a medical syringe infusion pump
(Model 22, Harvard Apparatus, USA).
1111 J. Metzger, K.-H. Wiesmuller, R. Schaude, W. G. Bessler, G. Jung, Int. J.
Peptide Protein R e x 1991, 37, 46.
[12] I. Metzger, G . Jung. Angew. Chem. 1987, 99, 343; Angew Chem. f n l . Ed.
resents a generally useful strategy and coincides with our
program directed towards the synthesis of glycosidase inhibitors.[*] We took the transformation of the diol2 to the
oxazolidinone 3 as our model reaction [Eq. (b)] for the general problem. This cyclization seemed to be a stringent test
because a rather low enantiomeric excess (ee) was observed
using BINAP0,'91 an asymmetric ligand that has proven to
be rather successful in a related case.[7281
In designing ligands, ease of accessibility is a major criterion. The ready availability of 2-diphenylphosphinobenzoic
acid (4) by Wurtz coupling of sodium 2-chlorobenzoate and
sodium diphenylphosphide (from sodium and triphenylphosphane)["' and of chirdl alcohols and amides makes the
Engl. 1987, 26, 336.
[13] F. Hillenkamp, Proc. 38th A S M S Conf Muss Specrrom. Allied Topics
(Tucson, A Z , 19901, p. 8.
[14] W. Beck, J. W. Metzger, K.-H. Wiesmiiller, A. Surovoy, B. Haas, G. Jung
in Innovation & Perspecfives in Solid Phase Synthesis & Relafed Terhnologies (Proc. 2nd In(. Sjmp. Canterbury, Englund, 19911 (Ed.: R. Epton)
Intercept, Andover, 1992, in press.
(151 J. Metzger, K.-H. Wiesmiiller, G. Jung, Znt. .
IPept. Protein Res. 1991, in
press.
[16] M. Sakairi, H. Kambara, Anal. Chem. 1989, 61, 1159.
(171 A. G. Beck-Sickinger, J. W. Metzger in Pepfide.y: Chemistry and Biology
(Proc. 12fh An?. Pepride Symp.. Boston. M A , 1991) (Eds.: J. A . Smith,
J. E. Rivier), Escom, Leiden, 1992, in press.
[IS] J. W. Metzger, M. Jung. D. Schmalzing, E. Bayer, V. Schnrig, Carbohydr.
Res. 1991, 222, 23.
228
0 VCH
Verlagsgesellschaft mbH. W-6940 Weinheim. 1992
[*] Prof. B. M. Trost, D. L. Van Vranken
I**]
Department of Chemistry
Stanford University
Stanford, CA 94305 (USA)
We thank the National Science Foundation (Graduate fellowship for
DLvV) and the General Medical Sciences Institute of the National Institutes of Health (NIH) for their generous support of our programs. Mass
spectra were provided by the Mass Spectrometry Facility, University of
California-San Francisco, supported by the NIH Division of Research
Resources.
0S70-0833/92/0202-0228$3.S0+.25/0
Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2
corresponding esters and amines attractive potential ligands.
Furthermore, by varying the length of the tether in bidentate-type ligands, the "bite angle" 0 in 1 [Eq. (a)] can be
modified. Opening this angle pushes the chiral environment
of the ligands towards the reacting ally1 system and could
enhance asymmetric induction.[7]
The importance of ligands possessing C, symmetry for
many asymmetric reactions" '1 led to the synthesis of a series
of potential bidentate diesters from C,-symmetric diols. Diamides from C,-symmetric diamines were also particularly
desirable as ligands because the amide linkage makes them
more rigid than esters. The availability of the corresponding
diols and diamines in enantiomerically pure form provided
diverse array of chiral ligands and [ (dba),Pd,]
CHCI, (dba = dibenzylideneacetonate) (see Table 1). Several noteworthy trends appear. The good to excellent ee's contrast with ee's of 5-15% obtained with monodentate and
non-C,-symmetric polydentate ligands. Curiously, changing
I
Table 1. Catalysis using chiral 2-(diphenylphosphino)benzoyl esters and
amides as ligands [a].
5
6
7
8
9
10
11
12c
1
8
9
1.5
1
5
2
0.33
0
0 to 20
-8 t o 2 0
0 to 5
0
20
0 to 5
0
100
98
100
97
97
87
68
94
+
+
+
83.9 ( f . 3 )
86.2 (k.3)
90.7 ( f . 1 )
+110.0 ( i . 7 )
f112.6 (k.3)
- 56.9 (k.2)
-105.9 ( k . 3 )
-124.2 (k.1)
3.90
2.40
2.49
0.99
3.12
3.05
2.82
3.41
60
61
64
78
80
40
75
88
[a] All reactions were run with 0.05equiv Pd(o) in THE [b] [a], = 141
( c = 2.52, CH,CI,) for enantiomerically pure oxazolidinone; ee determined by
'H NMR of the (+)-0-methylmandelate esters of the hydrolyzed product.
the distance between the two esters by modifying the precursors from a 1,2 (7)to a 1,4 (6)or a 1,5 diol (5) showed little
variation in ee. On the other hand, increasing conformational rigidity by going to the flat tartrimide 11 or the less flexible
amides 8 and 9 provides excellent yields of oxazolidin-2-one
with high asymmetric induction at reasonable operating
temperatures. Part of the increased ee observed with the
tartrimide 11 may derive from increasing 0 in 1 by an enlarged dihedral angle between the acyloxy substituents imposed by the flat ring.
Applying these arguments on the influence of conformation to the amides, which offer higher rigidity, led to the
design of the bisamide 12c. It is synthesized by the standard
acylation of optically pure diamine 12 b which, in turn,
of the known optiderives from a Curtius
Indeed, cyclization proceeded in
cally active diacid 12
excellent yield with the highest ee obtained so far in this
cyclization.
The absolute configuration of the product was determined
from the 0-methylmandelate ester["] of the hydrolyzed hydroxytosylamide, as was the enantiomeric purity. The configurations were established as (R,S) for the levorotatory
isomer of 3 and (S,R) for the dextrorotatory isomer. Ligands 5-9 all produced (S,R)-3 and ligands 10-12 all produced (R,S)-3. If one views the ligands along the principal
axis between the two stereogenic centers as drawn, the phosphine substituents are arranged in a clockwise (CW) helical
sense as in 13 for ligands 10-12 and in a counterclockwise
(CCW) helical sense for ligands 5-9. The clockwise arrangement of the ligand induces ionization of the prochiral leaving
group by a clockwise rotation of the palladium in 15 and vice
versa.
4
0
NH
PPh,
7
8
9
10
dNH
12a, R = C02H
12 b, R = NHZ
12c,R=
PPh,
ready access to ligands 5-11 and 1 2 1 2 ~by
' ~dicyclohexylcar~
bodiimide (DCC) coupling (catalytic amounts of 4-dimethylaminopyridine (DMAP), THF, room temperature) with the
acid 4. We performed our selected reaction [Eq. (b)] with this
A n g w . Chem. I n t . Ed. Engl. 31 (1992j No. 2
0 VCH
Verlugsgesellschuft mbH, W-6940 Weinheim. 1992
0570-0833/92/0202-0229$3.50+ ,2510
229
Hayashi; A. Yamamoto; Y. Ito, Tetrahedron Lett. 1988,29,99;T. Hayashi;
A. Yamamoto; Y. Ito, Chem. Lett. 1987, 177; T. Hayashi; A. Yamamoto;
T. Hagihara; Y Ito. Tetrahedron Lett. 1986, 27, 191.
D. Miiller, G. Umbrieht, B. Weber, A. Pfaltz, Helv. Chim. Acra. 1991, 74,
232; M. Yamaguchi, T. Shima, T. Yamagishi, M. Hida, Tetrahedron Lett.
1990, 3f, 5049; R. L. Halterman; H. L. Nimmons, Organometallics 1990,
9, 273; P. 9 . Mackenzie, J. Whelan, B. Bosnich, J. Am. Chem. Soc. 1985,
107, 2046; P.R. Auburn, P. B. Mackenzie, B. Bosnich, J. Am. Chem. Soc.
1) KzCO3, CHBOH,H20
quant.
t
2)
87% ee
CH31)
[a]? +69
PhAC02H
(C -1.77,
CHzC12)
DCC, DMAP
CH&2
quant.
The high asymmetric induction observed with these new
classes of ligands appears to be more general. The conversion of the diol 16['61to its oxazolidin-2-one 17 using diamide 9 provides 87 % ee of the enantiomer depicted (determined by conversion to the mandelate 22). The high ee
observed here compared to that of the cyclization of 2 with
the same ligand may arise because a six-membered ring is
more inflexible than a five membered ring.
The strategy described herein offers wide scope in the design of asymmetric ligands for transition-metal-catalyzed reactions. In palladium-catalyzed allylic alkylation, a reaction
in which asymmetric induction previously proved difficult to
achieve, these ligands are highly effective. Many questions
remain-the most prominent is whether these ligands are
serving as chelating ligands. Two facts support a bidentate
coordination. Firstly, a high ee is obtained when virtually
equimolar quantities of ligand and palladium are used. Secondly, a C,-symmetric ligand from isomannide which for
steric reasons can act as a bidentate ligand only with difficulty effects cyclization with only low ee. An advantage of these
ligands is the versatility for rational modification in the chiral scaffold independent of the phosphine substituents. Indeed, the ethanoanthracene ligand 16 was developed after
identification of some of the structural parameters that appeared important for asymmetric induction in our allylic
alkylations.
Received: September 12, 1991 [Z 4912 IE]
Getmdn version: Angew. Chem. 1992, 104, 194
CAS Registry numbers:
2, 29783-26-4; ( R , 9 - 3 , 13860423-6; (S,R)-3, 138604-24-7; 5, 138517-58-5; 6,
138517-59-6; 7,138517-60-9; 8,138517-61-0; 9,138517-62-1; 10,138517-63-2;
11, 138517-64-3; 12a, 33216-00-1; IZb, 138517-66-5; 12c, 138517-65-4; 16,
101312-33-8; 17, 238540-73-5; 18. 138517-67-6; TsN=C=O, 4083-64-1; (5')PhCH(CH,O)CO,H, 26164-26-1; (dba),Pd,, 51364-51-3.
[1] For most recent general reviews, see K. Tomioka, Synthesis 1990, 541 ; R.
Noyori; M. Kitamura, Modern Syn. Methods 1989. 5, 115; 1. Ojima, N.
Clos, C. Bastos, Tetrahedron 1989, 45, 6901; S . L. Blystone, Chem. Rev.
1989,89,1663; H. Kagan, Bull. SOC.
Chim. France 1988,846;H. Brunner,
Synthesis 1988, 645.
[2] For some recent reviews, see R. Noyori; H, Takaya, Ace. Chem. Res. 1990,
23,345; J. M. Brown, Angen,. Chem. Int. Ed. Engl. 1987,26,190; V. Caplar,
G. Comiso, V. Sunjic, Synthesis 1981, 85.
[3] For some recent reviews, see K. A. Jorgensen Chem. Rev. 1989,89,431;A.
Pfenninger, Synthesis 1986, 89. See also B. H. McKee, D. G. Gilheany,
B. K. Blackburn, K. B. Sharpless, Tetrahedron Lett. 1990,3f, 3817; H. L.
Kwong, C. Sorato, Y. Ogino, H. Chen, K. B. Sharpless, Tetrahedron Lett.
1990, 31,2999 and earlier papers in this series.
[4] G. Consiglio, R. M. Waymouth, Chem. Rev. 1989, 89, 257.
[5] T. Hayashi, A. Yamamoto, Y. Ito, Tetrahedron Lett. 1988, 29, 669; T.
230
0 VCH
Verlagsgesellschaft mbH. W-6940 Weinheim. 1992
1985, f07.2033.
9 . M. Trost, D. J. Murphy, Organometallics 1985, 4, 1143; B. M. Trost,
P. E. Strege, J. Am. Chem. Soc. 1977, 99, 1649.
B. M. Trost, D. L.VanVranken,J. Am. Chem. Soc. 1990, ff2,1261; B.M.
Trost, D. L. Van Vranken, J. Am. Chem. Soc. 1991, 113, 6317.
R. H. Grubbs, R.A. DeVries, Tetrahedron Lett. 1977, 26, 1879.
J. E. Hoots, T. 9. Rauchfuss, D. A. Wrobleski, Inorg. Syn. 1982, 21, 178.
J. K. Whitesell, Chem. Rev. 1989, 89, 1581.
For the diol precursors of 6: N. Baggett, P. Stribblehill, J. Chem. SOC.
Perkin 1977,1123;of 10: M. Kawashima, A. Hirayama, Chem. Lett. 1990,
2299; of 14: C. M. Wong, J. Buccini, J. Tekaa, Can. J. Chem. 1986,46,3091.
For the diamine precursor of 9: P. Manganey, T. Tejero, A. Alexakis, F.
Grosjean, I. Normant, Synthesis 1988,255; K. Saigo, N. Kubota, S. Takebdyashi, M. Hasegawa, Bull. Chem. Soc. Jpn. 1986,59,931; E. J. Corey, R.
Imwinkelried, S. Pikul, Y. B. Xiang, J. Am. Chem. SOC.1989, f f f , 5493.
The diol precursor of 5 was obtained by heating commercially available,
optically pure styrene epoxide (6 equiv) with 1 equiv of benzylamine at
120".
[13] See D. E. Homing, J. M. Muchowski, Can. J. Chem. 1967, 45, 1247.
[I41 W. E. Bachmann, C. B. Scott, J. Am. Chem. Soc. 1948, 70, 1458; M.-J.
Brienne, J. Jacques, Bull Soc. Chim. France 1973, 190; S. Hagashita, K.
Kuriyama, Tetrahedron 1972, 28, 1435.
[15] B. M. Trost, J. M. Belletire, S . Godleski, P. G. McDougal, . M. Balkovec,
J. J. Baldwin, M. E. Christy, G. S . Ponticello, S.L. Varga, J. P. Springer, J.
Org. Chem. 1986,512, 370.
[I61 A. P. Marchand, R. W. Allen, J. Org. Chem. 1974, 39, 1596; A. P.
Marchand, W. D. LaRoe, G. V. Madhava Sharma, S . Chander Suoi, D.
Sivakumar Reddy, J. Org. Chem. 1986, 51, 1622.
Spontaneous Self-Assembly of a Dinickel(r1)
Double Helicate Containing a 1,3-Benzenediyl
Spacer Group
By Edwin C. Constable,* Michael J: Hannon,
and Derek A . Tocher
Molecular species exhibiting a double-helical topology attract the chemist because of their inherent beauty and the
synthetic challenge of controlling the twisting of the component strands.*'] There has been considerable recent interest in
the utilization of the specific coordination requirements of
metal ions to control the assembly of such species.['- 31
Simply mixing suitable ligands with compatible metal ions
results in the spontaneous self-assembly of polynuclear
double-helical arrays. A helicating ligand must contain two
or more separate polydentate metal-binding sites which are
either directly linked or are connected by a suitable spacer
group.[31We have been particularly interested in developing
ligands in which the twisting of molecular threads occurs
about interannular C-C bonds between aromatic rings
(Scheme
We now describe a new class of helicating
ligand (1) containing a 1,3-benzenediyl spacer group.
[*] Dr. E. C. Constable, M. J. Hannon
Cambridge Centre for Molecular Recognition
University Chemical Laboratory
Lensfield Road, GB-Cambridge, CB2 1 EW (UK)
Dr. Derek A. Tocher
Department of Chemistry
University College London
20 Gordon Street, GB-London WC 1H OAJ (UK)
[**I This work was supported by the U.K. Science and Engineering Research
Council, Ciba-Geigy AG (studentship for MJH), and the Royal Society of
Great Britain.
0570-0833/92/0202-0230S 3.50+ .25/0
Angew. Chem. Int. Ed. Engl. 3f (1992) No. 2
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asymmetric, reaction, diols, metali, symmetries, diphenylphosphinobenzoyl, transitional, derivatives, ligand, diamine, catalyzed
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