New amino-, imino- and oxazolinosphosphites based on 1,1′-bi-2-naphtol: Coordination and catalytic properties

Article abstract of DOI:10.1016/S0022-328X(02)01561-9

A series of the new chiral BINOL-based phosphite P,N-hybrid ligands was prepared. The coordination behavior of all the ligands was studied and the neutral complexes [Rh(CO)Cl(P N)] were synthesized in order to characterize a degree of the electronic non-symmetry of donating centers. Also the neutral and cationic complexes cis-[PdCl₂(η²-P N=)], cis-[PdCl₂(η¹-P N=)₂], cis-[PdCl(η²-P N=) (η¹-P N=)]⁺Cl^-,[Pd(allyl)(η²-P N=)]⁺X^- (X^- = Cl^-, BF₄^-) were obtained and characterized. The new P,N-hybrid ligands gave up to 81% ee in the enantioselective Pd-catalyzed alkylation of 3-penten-2-yl carbonate by dimethyl malonate and up to 60% ee in the Rh-catalyzed hydrosilylation of acetophenone and acetylferrocene by diphenylsilane.

Full text of DOI:10.1016/S0022-328X(02)01561-9

Journal of Organometallic Chemistry 655 (2002) 204Á217
/
www.elsevier.com/locate/jorganchem
New amino-, imino- and oxazolinophosphites based on 1,1?-bi-2-
naphtol: coordination and catalytic properties
K.N. Gavrilov a, O.G. Bondarev b, R.V. Lebedev b, A.I. Polosukhin b, A.A. Shyryaev a,
S.E. Lyubimov a, P.V. Petrovskii b, S.K. Moiseev b, V.N. Kalinin b, N.S. Ikonnikov b,
V.A. Davankov b, A.V. Korostylev c,*
a Department of Chemistry, Ryazan State Pedagogic University, 46, Svoboda str., Ryazan 390000, Russia
b Institute of Organoelement Compounds, Russian Academy of Sciences, 28, Vavilova str., Moscow 119991, Russia
c Institut fur Organische Katalyseforschung an der Universitat Rostock e.V., Buchbinderstrasse 5-6, D-18055 Rostock, Germany
¨
¨
Received 9 November 2001; received in revised form 26 February 2002; accepted 29 April 2002
Abstract
A series of the new chiral BINOL-based phosphite P,N-hybrid ligands was prepared. The coordination behavior of all the ligands
was studied and the neutral complexes [Rh(CO)Cl(PfflN)] were synthesized in order to characterize a degree of the electronic non-
symmetry of donating centers. Also the neutral and cationic complexes cis-[PdCl2(h2-PfflNÄ
/
)], cis-[PdCl2(h1-PfflNÄ
/
)2], cis-
Clꢁ, BFꢁ4 ) were obtained and characterized. The new P,N-
[PdCl(h2-PfflNÄ
/
)(h1-PfflNÄ
/
)]ꢀClꢁ, [Pd(allyl)(h2-PfflNÄ
/
)]ꢀXꢁ (Xꢁ ꢂ
/
hydrid ligands gave up to 81% ee in the enantioselective Pd-catalyzed alkylation of 3-penten-2-yl carbonate by dimethyl malonate
and up to 60% ee in the Rh-catalyzed hydrosilylation of acetophenone and acetylferrocene by diphenylsilane. # 2002 Elsevier
Science B.V. All rights reserved.
Keywords: P,N-ligands; Phosphites; Rhodium complexes; Palladium complexes; Pd-catalyzed allylation; Rh-catalyzed hydrosilylation
1. Introduction
the P,S-bidentate phosphites gave up to 81% ee in the
Pd-, Rh- and Ir-catalysed allylic alkylation reactions
[11].
A notable series of the P,N-bidentate phosphite-
oxazolines (1) was successfully applied in the Pd-
catalyzed allylic alkylation (up to 96% ee) and Cu-
catalyzed 1,4-addition of diethylzinc to cyclic enones (up
to 96% ee) [9,12,13].
In the last 10 years (R)- and (S)-1,1?-bi-2-naphtol
(BINOL) proved to be useful building blocks in the
synthesis of chiral phosphite ligands. P-mono-, P,P-
bidentate phosphites and P,P-bidentate phosphinopho-
sphites derived from BINOL were successfully used in
the enantioselective catalysis [1Á9]. Far less frequently
/
hetero-bifunctional systems, i.e. systems possessing an-
other donor atom (e.g. O, S or N) besides the
phosphorus atom have been employed, although the
Finally, synthesis and application of the four chiral
BINOL based phosphites 2aÁd in the Cu-catalyzed
/
conjugate addition of Et2Zn to 2-cyclohexene-1-one
(up to 51% ee) and in the Pd-catalyzed substitution of
1,3-diphenyl-1,2-propenyl acetate by dimethyl malonate
P,O-ligands were found to give 70Á/71% ee in the Cu-
catalyzed addition of diethylzinc to chalcone [10], and
(up to 37% ee) were recently reported [14Á17].
/
The present paper aims at obtaining novel P,N-
bidentate phosphite derivatives of BINOL bearing
amino, imino and oxazoline functionalities and at
studying of their complexation and catalytic properties.
* Corresponding author. Tel.: ꢀ
/
49-381-4669334; fax: ꢀ49-381-
/
4669324.
E-mail address: andrei.korostylev@ifok.uni-rostock.de (A.V.
Korostylev).
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 5 6 1 - 9

K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á
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217
205
2. Experimental
and BINOL were dried in vacuum (2 mmHg, 3 h)
immediately before use.
Iminoalcohols 4i, 4j were synthesized analogously to
the known procedures [32].
2.1. General comments
All reactions were performed under Ar in dehydrated
solvents.
2.1.1. (2S,3S)-2-[(4-Dimethylamino-benzylidene)-
amino]-3-methyl-pentan-1-ol (4i)
IR spectra were recorded on a Specord M80 or
Nicolet 750 instrument. 31P-, 13C-, 1H-, 11B-, 19F-
NMR spectra were recorded on a Bruker AMX-400
instrument (162.0 MHz for 31P; 100.6 MHz for 13C,
Yellow viscous oil, 63% yield. [n]2D0 ꢂ1:4411ꢀ: B.p.
165Á
167 8C (0.8 mmHg, Kugelrohr distillation). 13C-
NMR (CDCl3): dC CH3 10.63, 15.15; CH2 25.10; CH
36.16; N(CH3)2 39.51; CH2O 63.59; CHN 76.59; CHAr
/
1
400.13 MHz for H, 128.34 MHz for 11B, 376.31 MHz
1
161.27. H-
for 19F). The complete assignment of all the resonances
in 13C-NMR spectra was achieved using DEPT techni-
ques. Chemical shifts (ppm) are given relative to Me4Si
110.86, 129.33; CAr 123.58, 151.33; CHÄ
/
NMR (CDCl3): dH (J(H,H), Hz) 8.08 (s, 1H, CHÄ
/),
7.57 (d, 2H, 3J 8.8, HAr), 6.67 (d, 2H, 3J 8.8, HAr), 3.78
3
(m, 2H, CH2O), 3.00 (s, 6H, N(CH3)2), 2.98 (m, 1H, J
(1H- and 13C-NMR), 85% H3PO4 (31P-NMR), BF3×
/
Et2O (11B-NMR), CF3COOH (19F-NMR). Mass spec-
tra were recorded on a Kratos MS 890 spectrometer
(EI), MSVKh TOF spectrometer with ionization by
californium-252 fission fragments (plasma desorption
technique). Electrospray mass spectra (ES MS) were
measured on a Micromass BioQ II-ZS mass spectro-
8.8, NCH), 2.41 (s, br, 1H, OH), 1.69 (m, 1H, CH2), 1.46
3
(m, 1H, CH2), 1.04 (m, 1H, CH), 0.92 (d, 3H, J 6.8,
CH3), 0.83 (t, 3H, 3J 7.6, CH3). Anal. Calc. for
C15H24N2O: C, 72.54; H, 9.74; N, 11.28. Found: C,
72.83; H, 10.02; N, 11.00%.
2.1.2. (2S,3S)-2-[(Ferrocenylidene)-amino]-3-methyl-
pentan-1-ol (4j)
meter. Organometallic compound solutions at 5Á
pmol mlꢁ1 in THF or MeCN were infused via a Harvard
Apparatus Model 11 syringe pump at 5 ml minꢁ1
Spectra were recorded over a mass range of 200Á1200
Da and were calibrated relative to a mixed PEG
standard. Sedimentation analyses were performed on a
MOM-3180 analytical ultracentrifuge according to pub-
lished techniques [18,19]. Elemental analyses were
performed at the Laboratory of Microanalysis (Institute
of Organoelement Compounds, Moscow).
/
10
Orange solid, 81% yield. 1H-NMR (CDCl3): dH
.
(J(H,H), Hz) 8.06 (s, 1H, CHÄ
/
), 4.72 (m, 1H, Fc),
4.51 (m, 1H, Fc), 4.37 (m, 1H, Fc), 4.34 (m, 1H, Fc),
/
3
4.10 (s, 5H, Fc), 3.82 (m, 2H, CH2O), 2.94 (m, 1H, J
8.8, NCH), 1.65 (m, 1H, CH), 1.24 (m, 1H, CH2), 0.94
3
3
(d, 3H, J 6.8, CH3), 0.88 (t, 3H, J 7.6, CH3). 13C-
NMR (CDCl3): dC (J(C,P), Hz) CH3 10.76, 15.35; CH2
25.67; CH 30.03; CH2O 63.79; CFc 66.97, 68.69, 69.85,
70.17, 70.32; CHN 77.85; CFc 79.97; CHÄ
/
161.91. Anal.
[Rh(CO)2Cl]2 [20], [PdCl2(COD)] [21], [PdCl(allyl)]2
[22], [PdCl2(CH3CN)2] [23], amino- and iminoalcohols
4c [24], 4d [25], 4f [26], 4h [27], 4k [28], 4l [29], 4m [30]
and chlorophosphite 3 [31] were synthesized according
to the known procedures. Compounds 4a (Fluka), 4b
(Aldrich), 4e (Aldrich), 4n (Fluka), rac-, (R)- and (S)-
BINOL (Fluka) were commercially available. Amino-
and iminoalcohols 4g (quincoridine, Buchler GmbH),
Calc. for C17H23FeNO: C, 73.66; H, 4.79; N, 4.47.
Found: C, 73.75; H, 5.01; P, 4.18%.
2.2. Preparation of ligands
2.2.1. General technique
A solution of the corresponding alcohol (3.5ꢃ
mol) and Et3N (0.36 ml, 3.5ꢃ
10ꢁ3 mol) in C6H5CH3
(20 ml) was added dropwise at 0 8C to a stirred solution
/
10ꢁ3
4c, 4eÁ
/
f, 4hÁ
/
i, 4k were azeotropically dried with C6H6
b, 4d, 4j, 4lÁ
/
and distilled before use. Compounds 4aÁ
/
/
n

206
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/
of chlorophosphite (3) (1.227 g, 3.5ꢃ
/
10ꢁ3 mol) in
CAr 121.67Á148.80). MS (EI, 70 eV): m/z (I, %) 457 (2,
/
C6H5CH3 (15 ml). The reaction mixture was warmed to
60 8C, stirred for 1 h and left at 20 8C overnight. Then
the solution was filtered and C6H14 (30 ml) was added to
[M]ꢀ), 428 (4), 387 (4), 332 (45), 286 (54), 268 (47), 125
(34). Anal. Calc. for C28H28NO3P: C, 73.51; H, 6.17; P,
6.77. Found: C, 73.76; H, 6.00; P, 6.98%.
precipitate NEt3×
/
HCl. The mixture was filtered again,
the solvent evaporated in vacuum and the residue dried
in high vacuum to give the desired product.
2.2.8. (2?S)-2-[(1?-Methyl-pyrrolidinyl-2?)-
methoxy]dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5e)
White solid, 89% yield. 31P-NMR (CDCl3): dP 140.52,
2.2.2. (1?S,2?R)-2-(1?-Benzyl-3?-dimethylamino-2?-
methyl-1?-phenyl-propoxy)dinaphtho[2,1-d:1?,2?-
f](1,3,2) dioxaphosphepine (5a)
Yellow solid, 89% yield. 31P-NMR (CDCl3): dP
152.03, 151.02. 13C-NMR (CDCl3): dC (J(C,P), Hz)
CH3 14.47, 14.92; CH 40.53, 43.97 (3J 9.5); CH2Ph
44.87 (3J 8.0), 45.15 (3J 9.5); N(CH3)2 45.53, 45.69;
140.62. 13C-NMR (CDCl3): dC
27.70, 27.78; NCH3 40.91, 40.95; NCH2 57.12; NCH
Ã
/
(CH2)2Ã
/
22.41, 22.48,
64.97; OCH2 66.23; CAr 114.76Á153.10. MS (EI, 70 eV):
/
m/z (I, %) 429 (2, [M]ꢀ), 332 (74), 286 (100), 97 (21).
Anal. Calc. for C26H24NO3P: C, 72.72; H, 5.63; P, 7.21.
Found: C, 72.49; H, 5.37; P, 6.96%.
NCH2 60.63, 60.42; OCPh 88.28, 88.80; CAr 121.51Á
/
147.84. MS (EI, 70 eV): m/z (I, %) 382 (2), 332 (8),
268 (14), 267 (5), 58 (100). Anal. Calc. for C39H36NO3P:
C, 78.37; H, 6.07; P, 5.18. Found: C, 78.42; H, 6.10; P,
5.25%.
2.2.9. (2?S)-2-[(1?-Benzyl-pyrrolidinyl-2?)-
methoxy]dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5f)
White solid, 93% yield. 31P-NMR (CDCl3): dP 144.06,
144.72. 13C-NMR (CDCl3): dC
CH2Ph 54.02; NCH2 59.02; NCH 63.16; OCH2 66.89;
Ã
/
(CH2)2Ã
/
22.65, 27.60;
2.2.3. (Rax)-5a
Yellow solid, 87% yield. 31P-NMR (CDCl3): dP
CAr 121Á148.35. MS (EI, 70 eV): m/z (I, %) 505 (14,
/
152.03.
[M]ꢀ), 414 (32), 332 (38), 268 (100), 174 (70). Anal.
Calc. for C32H28NO3P: C, 76.03; H, 5.58; P, 6.13.
Found: C, 75.84; H, 5.29; P, 6.25%.
2.2.4. (1?R,2?S)-2-(2?-Dimethylamino-1?-phenyl-
propoxy)[2,1-d:1?,2?-f](1,3,2) dioxaphosphepine (5b)
White solid, 94% yield. 31P-NMR (CDCl3): dP 147.24;
151.44. 13C-NMR (CDCl3): dC CH3 21.20, 22.74;
N(CH3)2 41.62; NCH 64.68, 65.75; OCH2 77.83; CAr
2.2.10. (2?R,4?S,5?R)-2-[(5?-Vinylquinuclidyl-
2?)methoxy]dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5g)
White solid, 85% yield. 31P-NMR (CDCl3): dP 142.36,
142.43. 13C-NMR (CDCl3): dC (J(C,P), Hz) CHCH2CH
22.91, 23.12; CH2CH2CH 26.07, 26.19; CH2CHCH2
118.79Á153.25. MS (EI, 70 eV): m/z (I, %) 448 (1), 422
/
(97), 268 (100), 252 (7). Anal. Calc. for C31H28NO3P: C,
75.44; H, 5.72; P, 6.28. Found: C, 75.62; H, 5.51; P,
6.11%.
27.14, 27.25; CHCHCHÄ
46.98; NCH2CH2 48.47, 48.57; CHN 55.54, 55.60 (3J
2.9); OCH2 64.97 (2J 3.5), 65.19 (2J 2.4); CH2Ä
114.15,
114.21; CHÄ 139.67, 139.87; CAr 121.46Á148.40. MS
/
39.13, 39.29; NCH2CH 46.92,
2.2.5. (Rax)-5b
White solid, 93% yield. 31P-NMR (CDCl3): dP 151.44.
/
/
/
(EI, 70 eV): m/z (I, %) 332 (35), 286 (100), 268 (37), 167
(10). Anal. Calc. for C30H28NO3P: C, 74.83, H, 5.86; P,
6.43. Found: C, 74.56; H, 5.99; P, 6.66%.
2.2.6. (2?R)-2-(2?-Dibenzylamino-3?-methyl-
butoxy)dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5c)
White solid, 92% yield. 31P-NMR (CDCl3): dP 142.01,
142.53. 13C-NMR (CDCl3): dC (J(C,P), Hz) CH3 20.10,
20.92; CH 27.40; NCH2 54.59; NCH 62.90; OCH2 63.80;
2.2.11. (2?R,Sax)-2-{2?-[(4-Dimethylamino-
benzylidene)-amino]-3?-methyl-butoxy}dinaphtho[2,1-
d:1?,2?-f](1,3,2) dioxaphosphepine ((Sax)-5h)
CAr 121.50Á148.98. MS (EI, 70 eV): m/z (I, %) 554 (1),
/
White solid, 94% yield. 31P-NMR (CDCl3): dP 145.01.
13C-NMR (CDCl3): dC (J(C,P), Hz) CH3 18.73, 19.69,
CH 29.84; N(CH3)2 40.06; OCH2 67.24 (2J 8.0); NCH
332 (90), 268 (94), 91 (100). Anal. Calc. for
C39H36NO3P: C, 78.37; H, 6.07; P, 5.18. Found: C,
78.53; H, 5.84; P, 5.30%.
76.73 (3J 4.1); CAr 111.42Á
/
151.83; CHÄ/N 161.47. MS
(EI, 70 eV): m/z (I, %) 748 (100), 415 (3), 332 (89), 315
(7), 286 (57), 268 (97), 252 (7), 216 (7), 203 (33). Anal.
Calc. for C34H33N2O3P: C, 74.44; H, 6.06; P, 5.65.
Found: C, 74.22; H, 6.18; P, 5.96%.
2.2.7. (2?R)-2-[2?-(N-
pyrrolidine)butoxy]dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5d)
White solid, 84% yield. 31P-NMR (CDCl3): dP 142.16,
142.78. 13C-NMR (CDCl3): dC (J(C,P), Hz) CH3 10.36;
10.37; CH2CH3 20.61; CH2 (cycl.) 23.21, 23.30; NCH2
49.84; OCH2 63.52 (2J 3.0), 63.60 (2J 2.5); NCH 64.65;
2.2.12. (Rax)-5h
White solid, 95% yield. 31P-NMR (CDCl3): dP 147.85.

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207
2.2.13. (2?S,3?S)-2-{2?-[(4-Dimethylamino-
benzylidene)-amino]-3?-methyl-pentyloxy}-
dinaphtho[2,1-d:1?,2?-f](1,3,2) dioxaphosphepine (5i)
White solid, 92% yield. 31P-NMR (CDCl3): dP 144.84,
147.42. 13C-NMR (CDCl3): dC (J(C,P), Hz) CH3 10.87,
10.94, 15.53, 15.59; CH2 25.23, 25.30; CH 36.39, 36.42;
N(CH3)2 40.06, 40.12; OCH2 67.07 (2J 7.8), 67.17 (2J
2.2.20. 2-{2?-[(Ferrocenylidene)-amino]-
phenoxy}dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5m)
Red solid, 90% yield. 31P-NMR (C6D6): dP 143.72.
13C-NMR (CDCl3): dC CFc 69.12, 69.42, 69.66, 71.36,
71.50; CFc(ipso) 80.23, CAr 118.06Á
/
148.05; CHÄ
/
160.62.
MS (EI, 70 eV): m/z (I, %) 619 (41, [M]ꢀ), 305 (100),
268 (37), 240 (66). Anal. Calc. for C37H26FeNO3P: C,
71.74; H, 4.23; P, 5.00. Found: C, 71.95; H, 4.53; P,
4.77%.
10.0); NCH 75.78 (3J 4.2), 75.92 (3J 2.2); CAr 111.43Á
151.93; CHÄN 161.43, 161.86. MS (EI, 70 eV): m/z (I,
%) 561 (1, [Mꢁ
H]ꢀ), 748 (100), 332 (92), 315 (10), 286
/
/
/
(9), 268 (92), 252 (12), 231 (7), 217 (22), 161 (19), 147
(71). Anal. Calc. for C35H35N2O3P: C, 74.72; H, 6.27; P,
5.50. Found: C, 74.86; H, 6.11; P, 5.27%.
2.2.21. (4?S,5?S)-2-[(2?-Methyl-5?-phenyl-2?-oxazolino-
4?)methoxy]dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5n)
White solid, 90% yield. 31P-NMR (CDCl3): dP 139.18,
141.61. 13C-NMR (CDCl3): dC (J(C,P), Hz) CH3 13.95;
OCH2 65.33, 65.92 (2J 4.5); NCH 74.52 (3J 2.4), 74.62
2.2.14. (Rax)-5i
White solid, 91% yield. 31P-NMR (C6D6): dP 143.94.
(3J 2.0); OCH2(Ph) 82.67, 82.86; CAr 121.24Á
/148.45;
2.2.15. (Sax)-5i
White solid, 94% yield. 31P-NMR (C6D6): dP 144.82.
CÄ
/
N 165.89, 166.04. MS (EI, 70 eV): m/z (I, %) 505 (9,
[M]ꢀ), 332 (45), 315 (6), 286 (4), 268 (98), 252 (5), 174
(2). Anal. Calc. for C31H24NO4P: C, 73.66; H, 4.79; P,
6.13. Found: C, 73.44; H, 4.92; P, 6.07%.
2.2.16. (2?S,3?S,Rax)-2-{2?-[(Ferrocenylidene)-amino]-
3?-methyl-pentyloxy}dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine ((Rax)-5j)
Red solid, 88% yield. 31P-NMR (C6D6): dP 141.36.
13C-NMR (C6D6): dC (J(C,P), Hz) CH3 11.40, 15.92;
CH2 25.55; CH 36.71; CH2O 67.16; CFc 68.75, 69.16,
69.31, 70.30, 70.40; CHN 76.54 (3J 3.0); CFc(ipso) 81.41;
2.2.22. (Rax)-5n
White solid, 88% yield. 31P-NMR (C6D6): dP 142.34.
2.2.23. (Sax)-5n
White solid, 90% yield. 31P-NMR (C6D6): dP 139.49.
CAr 122.08Á
/
149.65, CHÄ
/
161.16. MS (EI, 70 eV): m/z
(I, %) 627 (4, [M]ꢀ), 543 (100), 478 (85), 332 (39), 268
(95). Anal. Calc. for C37H34FeNO3P: C, 70.82; H, 5.46;
P, 4.94. Found: C, 71.08; H, 5.64; P, 5.14%.
2.3. Preparation of Rh complexes
2.3.1. General technique for complexes 6aÁ
/
b, 6dÁ
/
i, 6kÁ
/
l,
6n
2.2.17. (Sax)-5j
A solution of the corresponding ligand (3.6ꢃ
mol) in CH2Cl2 (20 ml) was added dropwise to a stirred
solution of [Rh(CO)2Cl]2 (0.070 g, 1.8ꢃ
10ꢁ4 mol) in
the same solvent (20 ml) at 20 8C. The reaction mixture
was stirred at 20 8C for 0.5 h. The excess of the solvent
was then removed in vacuum (40 mmHg), and 10 ml of
C6H14 was added to the residue. The precipitate
obtained was separated by centrifugation, washed up
/
10ꢁ4
Red solid, 87% yield. 31P-NMR (C6D6): dP 135.91.
/
2.2.18. (aR)-2-{2?-[Methyl(a-phenylethyl)-
imino]phenoxy}dinaphtho[2,1-d:1?,2?-f](1,3,2)
dioxaphosphepine (5k)
White solid, 80% yield. 31P-NMR (CDCl3): dP 144.94,
145.12. 13C-NMR (CDCl3): dC (J(C,P), Hz) CH3 24.61,
24.92; NCH 69.69, 69.75; CAr 116.80Á
/
151.10; CHÄ
/
N
with C6H14 (2ꢃ10 ml) and dried in vacuum (2 mmHg).
/
154.72, 154.79. MS (EI, 70 eV): m/z (I, %) 438 (18), 332
(22), 268 (28), 252 (5), 105 (100). Anal. Calc. for
C35H26NO3P: C, 77.91; H, 4.86; P, 5.74. Found: C,
78.20; H, 4.51; P, 5.99%.
2.3.2. Complex 6a
Yellow solid, 82% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) CH3 19.07, 19.38; CH 43.34 (3J 10.3),
44.67 (3J 9.9); CH2Ph 45.85, 45.98; N(CH3)2 47.22,
48.76, 51.16, 51.43; NCH2 69.15, 69.54; OCPh 91.69 (2J
2.2.19. (Sax)-2-{2?-[(Benzylidene)-
amino]phenoxy}dinaphtho[2,1-d:1?,2?-f](1,3,2)
8.1), 92.89 (2J 5.4); CAr 121.05Á
148.60. Anal. Calc. for
C40H36ClNO4PRh: C, 62.88; H, 4.75; P, 4.05. Found: C,
63.14; H, 4.86; P, 3.81%.
/
dioxaphosphepine ((Sax)-5l)
Yellow solid, 92% yield. 31P-NMR (CDCl3): dP
145.34. 13C-NMR (CDCl3): dC CAr 114.59Á
/147.80,
CHÄ
/
160.21. MS (EI, 70 eV): m/z (I, %) 511 (81,
2.3.3. Complex 6b
[M]ꢀ), 434 (32), 268 (100), 196 (85). Anal. Calc. for
C33H22NO3P: C, 77.49; H, 4.34; P, 6.06. Found: C,
77.27; H, 4.52; P, 6.38%.
Yellow solid, 90% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) CH3 13.89, 22.38; N(CH3)2 46.46, 48.45,
48.46, 49.29; NCH 71.48, 72.12; OCH2 76.73 (2J 4.5),

208
K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á217
/
77.48 (2J 9.2); CAr 120.52Á
C32H28ClNO4PRh: C, 58.24; H, 4.28; P, 4.69. Found:
C, 58.07; H, 4.57; P, 4.79%.
/
147.78. Anal. Calc. for
2.3.10. Complex 6k
Yellow solid, 98% yield. 13C-NMR (Me2SO-d6): dC
(J(C,P), Hz) CH3 22.25, 22.31; NCH 67.44, 67.77; CAr
114.83Á
/
152.92; CHÄ
/
N 163.17, 163.77. Anal. Calc. for
C36H26ClNO4PRh: C, 61.25; H, 3.71; P, 4.39. Found: C,
61.48; H, 3.93; P, 4.01%.
2.3.4. Complex 6d
Yellow solid, 96% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) CH3 10.29, 10.64; CH2CH3 22.48; CH2
(cycl.) 23.48, 24.01, 24.99; NCH2 59.32, 60.28; OCH2
2.3.11. Complex (Sax)-6l
Yellow solid, 88% yield. Anal. Calc. for
C34H22ClNO4PRh: C, 60.24; H, 3.27; P, 4.57. Found:
C, 59.95; H, 3.51; P, 4.73%.
65.59; NCH 71.88; CAr 120.98Á148.82. Anal. Calc. for
/
C29H28ClNO4PRh: C, 55.83; H, 4.52; P, 4.96. Found: C,
55.67; H, 4.64; P, 4.75%.
2.3.12. Complex (Sax)-6n
Yellow solid, 91% yield. Anal. Calc. for
C32H24ClNO5PRh: C, 57.20; H, 3.60; P, 4.61. Found:
C, 57.47; H, 3.83; P, 4.42%.
2.3.5. Complex 6e
Yellow solid, 93% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) Ã
45.61, 46.03; NCH2 59.25, 60.89; NCH 64.00 (3J 4.9);
OCH2 69.50, 69.63; CAr 113.92Á152.70. Anal. Calc. for
/
(CH2)2Ã
/
20.30, 21.61, 24.32; NCH3
2.3.13. Complex (Rax)-6n
Yellow solid, 90% yield.
/
C27H24ClNO4PRh: C, 54.43; H, 4.06; P, 5.20. Found: C,
54.71; H, 3.89; P, 5.03%.
2.3.14. Preparation of the complexes 6c, (Rax)-6j, 6m, 6n
Rh complexes with ligands 5c, (Rax)-5j, 5m, 5n were
synthesized for the NMR experiments as follows: a
2.3.6. Complex 6f
Yellow solid, 95% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) Ã
/
(CH2)2Ã
/
21.09, 22.54, 23.53, 24.58;
solution of L* (3.6ꢃ
added dropwise to a stirred solution of [Rh(CO)2Cl]2
(0.070 g, 1.8ꢃ
10ꢁ4 mol) in the same solvent (1.5 ml).
/
10ꢁ4 mol) in CDCl3 (1.5 ml) was
CH2Ph 57.80, 59.72; NCH2 60.75, 63.17; NCH 63.52
(3J 3.4), 64.78 (3J 5.5); OCH2 65.88 (2J 8.0), 67.04 (2J
/
6.3);
CAr
120.73Á
/
147.31.
Anal.
Calc.
for
Then, a 1 ml sample of the reaction solution was
transferred to a NMR tube and NMR experiment was
carried out.
C33H28ClNO4PRh: C, 58.99; H, 4.20; P, 4.61. Found:
C, 59.21; H, 4.43; P, 4.34%.
2.4. Preparation of Pd(II) complexes
2.3.7. Complex 6g
Yellow solid, 87% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) CHCH2CH 22.84; CH2CH2CH 25.56,
2.4.1. General technique for complexes (Rax)-7h and
(Sax)-7i
A solution of the corresponding ligand (2ꢃ
mol) in CH2Cl2 (15 ml) was added dropwise to a stirred
solution of [PdCl2(CH3CN)2] (0.052 g, 2ꢃ
10ꢁ4 mol) in
the same solvent (15 ml) at 20 8C. The reaction mixture
was stirred at 20 8C for 1 h. The excess of the solvent
was then removed in vacuum (40 mmHg), and 10 ml of
C6H14 was added to the residue. The precipitate
obtained was separated by centrifugation, washed with
26.37; CH2CHCH2 26.34, 26.37; CHCHCHÄ
NCH2CH 48.49, 48.57; NCH2CH2 50.69, 51.23; CHN
60.96 (3J 5.4), 62.30; OCH2 66.14 (2J 3.6), 66.66; CH2Ä
137.29; CAr 120.89Á147.55. Anal.
/
38.57;
/
10ꢁ4
/
/
115.88, 115.92; CHÄ
/
/
Calc. for C31H28ClNO4PRh: C, 57.47; H, 4.36; P, 4.78.
Found: C, 57.81; H, 4.46; P, 4.44%.
2.3.8. Complex (Sax)-6h
Yellow solid, 92% yield. 13C-NMR (CDCl3): dC CH3
18.13, 19.88; CH 31.34; N(CH3)2 39.28; OCH2 70.24;
ether (2ꢃ10 ml) and dried in vacuum (2 mmHg).
/
2.4.2. Complex (Rax)-7h
NCH 78.00; CAr 110.18Á
Calc. for C35H33ClN2O4PRh: C, 58.80; H, 4.65; P, 4.33.
Found: C, 58.63; H, 4.27; P, 4.63%.
/
153.17; CHÄ
/
N 170.41. Anal.
Yellow solid, 93% yield. IR (CsI, Nujol, cmꢁ1):
n(PdÃ
/
Cl) 342, 304. Anal. Calc. for C34H33Cl2N2O3PPd:
C, 56.25; H, 4.58; P, 4.27. Found: C, 56.58; H, 4.62; P,
4.01%.
2.3.9. Complex 6i
Yellow solid, 89% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) CH3 10.36, 10.51, 14.18, 14.28; CH2
25.37, 25.50; CH 37.56; N(CH3)2 39.71, 40.00; OCH2
2.4.3. Complex (Sax)-7i
Yellow solid, 95% yield. 13C-NMR (CDCl3): dC
(J(C,P), Hz) CH3 9.88, 13.46; CH2 25.24; CH 37.01;
N(CH3)2 39.77; OCH2 69.67 (2J 4.9); NCH 74.47; CAr
69.41 (2J 3.1), 70.52; NCH 76.43, 77.24; CAr 110.63Á
/
153.68; CHÄ
/
N 170.74, 171.10. Anal. Calc. for
C36H35ClN2O4PRh: C, 59.31; H, 4.84; P, 4.25. Found:
C, 59.36; H, 4.98; P, 4.02%.
111.05Á
/
155.88; CHÄ
/
N 171.65. IR (CsI, Nujol, cmꢁ1):
n(PdÃCl) 338, 300. Anal. Calc. for C35H35Cl2N2O3PPd:
/

K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á
/
217
209
C, 56.81; H, 4.77; P, 4.19. Found: C, 56.66; H, 5.00; P,
4.04%.
NMR (CDCl3): dF
ꢁ
/
73.87. 11B-NMR (CDCl3): dB
ꢁ
/
1.37. MS (PD): m/z (I, %) 774 (52, [Pd(allyl)L]ꢀ), 543
(39), 332 (100). Anal. Calc. for C40H39BF4FeNO3PPd:
C, 55.75; H, 4.56; P, 3.59. Found: C, 55.64; H, 4.28; P,
3.88%.
2.4.4. Complex (Rax)-8h
Complex (Rax)-8h was obtained using the mentioned
above for compounds 7h and 7i technique from (Rax)-5h
(0.219 g, 4ꢃ
/
10ꢁ4 mol) and [PdCl2(COD)] (0.057 g, 2ꢃ
/
2.4.9. Pd complexes with ligands 5b, (Rax)-5h and 5m
Pd complexes with ligands 5b, (Rax)-5h and 5m, were
synthesized for the NMR experiments as follows: a
solution of L* (10ꢁ4 or 2ꢃ
10ꢁ4 mol)
Yellow solid, 90% yield. MS (PD): m/z (I, %) 1238 (7,
[PdClL2]ꢀ), 1202 (10), 548 (37), 217 (100). Anal. Calc.
for C68H66Cl2N4O6P2Pd: C, 64.08; H, 5.22; P, 4.86.
Found: C, 63.94; H, 5.48; P, 4.56%.
/
10ꢁ4 mol) in CDCl3 (1.5 ml)
stirred solution of
was added dropwise to
a
[PdCl2(COD)] (0.0285 g, 10ꢁ4 mol) in the same solvent
(1.5 ml). Then a 1 ml sample of the reaction solution was
transferred to a NMR tube and NMR experiment was
carried out.
2.4.5. General technique for complexes (Rax)-9h and
(Sax)-9l
A solution of the corresponding ligand (4ꢃ
mol) in CH2Cl2 (20 ml) was added dropwise to a stirred
solution of [Pd(allyl)Cl]2 (0.073 g, 2ꢃ
10ꢁ4 mol) in the
/
10ꢁ4
2.5. Catalytic experiments
/
same solvent (20 ml) at 20 8C. The reaction mixture was
stirred at 20 8C for 1 h. The solvent was then removed
2.5.1. Pd-catalyzed alkylation of 3-penten-2-yl carbonate
with dimethyl malonate
in vacuum and the solid was washed up with C6H14 (2ꢃ
/
[Pd(p-allyl)Cl]2 (3.6 mg, 1ꢃ
/
10ꢁ5 mol) and the ligand
10 ml) and dried in vacuum (2 mmHg).
5 (2.2ꢃ 8ꢃ
/
10ꢁ5Á 10ꢁ5 mol) were dissolved in the
corresponding solvent (4 ml) and the mixture was stirred
/
/
2.4.6. Complex (Rax)-9h
at room temperature (r.t.) for 20 min. Then, 3-penten-2-
10ꢁ3 mol), dimethyl malonate
YellowÁ
/
orange solid, 92% yield. 13C-NMR (CDCl3):
yl carbonate (160 mg, 1ꢃ
/
dC (J(C,P), Hz) CH3 18.48, 18.97; CH 29.15; N(CH3)2
39.63; CH2 (allyl, trans-N) 57.00; OCH2 64.92 (2J 14.4);
NCH 78.42; CH2 (allyl, trans-P) 80.86 (2J 42.5); CH
(132 mg, 1.5ꢃ
/
10ꢁ3 mol), BSA (305 mg, 1.5ꢃ10ꢁ3
/
mol) and KOAc (2.5 mg) were added to the catalyst and
the reaction solution was stirred at r.t. for 24 h. The
reaction mixture was then poured into saturated aq.
(allyl) 121.10; CAr 111.08Á
/
153.96; CHÄ
/
N 168.04. MS
(PD): m/z (I, %) 713 (13, [Pd(allyl)L(H2O)]ꢀ), 695 (7,
[Pd(allyl)L]ꢀ), 654 (10), 548 (30), 217 (100). Anal. Calc.
for C37H38ClN2O3PPd: C, 60.75; H, 5.24; P, 4.23.
Found: C, 61.06; H, 5.53; P, 4.16%.
NH4Cl solution and extracted with ether (2ꢃ50 ml).
/
The combined organic extracts were washed with aq.
NaHCO3 and water dried (Na2SO4), filtered and con-
centrated in vacuum. Purification by flash chromato-
graphy (silica gel, petroleum etherÁEtOAc 8:1) gave the
allylic alkylation product as a colorless oil. The S
absolute configuration was ascribed to the product
/
2.4.7. Complex (Sax)-9l
YellowÁ
/
orange solid, 95% yield. 13C-NMR (CDCl3):
dC (J(C,P), Hz) CH2 (allyl, trans-N) 57.8, 62.11; CH2
based on the (ꢁ) sign of its optical rotation [33].
/
(allyl, trans-P) 81.00 (2J 22.3), 81.47 (2J 27.6); CH (allyl)
Enantiomeric excess was determined by chiral GC
(fused silica capillary column DP-TFA-g-CD, 90 8C,
He, 1.8 bar).
119.00, 120.31; CAr 111.16Á
/
152.45, CHÄ
/
162.27, 162.54.
MS (PD): m/z (I, %) 658 (72, [Pd(allyl)L]ꢀ), 617 (39),
315 (22), 269 (100). Anal. Calc. for C36H27ClNO3PPd:
C, 62.26; H, 3.92; P, 4.46. Found: C, 62.13; H, 4.15; P,
4.22%.
2.5.2. Rh catalyzed hydrosilylation of ketones 12a,b with
diphenylsilane
A mixture of [RhCl(COD)]2 (0.004 g, 8.1ꢃ
or [IrCl(COD)]2 (0.0054 g, 8.1ꢃ
10ꢁ6 mol) and the
ligand 5 (16.2Á64.8ꢃ
10ꢁ6 mol) in C6H5CH3 (2 ml) was
/
10ꢁ6 mol)
2.4.8. Complex (Rax)-10j
/
Complex (Rax)-10j was obtained using the mentioned
above for compounds 9h and 9l technique in THF. But,
before the evaporation of the reaction mixture, AgBF4
/
/
stirred at r.t. for 45 min. Then acetophenone (12a) or
acetylferrocene (12b) was added, the reaction mixture
was stirred for 5 min and cooled down to 0 8C. Cold
(0.078 g, 4ꢃ
/
10ꢁ4 mol) was added and the solution was
filtered
(0 8C) H2SiPh2 (0.2 ml, 10.8ꢃ
10ꢁ4 mol) was then
/
Red solid, 88% yield. 13C-NMR (C6D6): dC (J(C,P),
Hz) CH3 10.68, 16.00; CH2 25.63; CH 37.00; CH2 (allyl,
trans-N) 54.64; CFc 61.26, 62.00, 62.34, 62.70, 64.39;
CH2O 66.14 (2J 11.7); CFc(ipso) 75.61; CHN 77.10 (3J
3.4); CH2 (allyl, trans-P) 78.82 (2J 45.9); CH (allyl)
added neat and the mixture was stirred at 0 8C for 16 h
followed by addition of a solution of para-toluenesul-
fonic acid (1 mg) in MeOH (1 ml) (for 12a). The solution
was stirred over 4 h at r.t. and, in the case of 12a, excess
p-CH3C6H4SO3H was neutralized with NaHCO3. The
reaction mixture was evaporated. In the case of 1-
118.00 (2J 9.1); CAr 112.07Á
/
147.52; CHÄ
/
168.20. 19F-

210
K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á217
/
ferrocenylethanol (13b), the residue was purified as
published [34]; purification of 1-phenylethanol (13a)
was accomplished by Kugelrohr distillation (1 mmHg,
Table 1
IR data for compounds 6aÁ
/
n
Compound n(CO) (cmꢁ1
)
n(RhÃCl) (cmꢁ1) (Nujol)
90Á
ducts was finally determined by chiral GC (Chiraldex B-
DM, 30 mꢃ0.25 mm, He, 120 8C, 13a) or HPLC
/
95 8C). The enantiomeric composition of the pro-
(CHCl3)
(KBr)
/
6a
6b
2036
2038
2025
2035
2038
2035
2036
2022
2026
2030
2036
2042
2038
2036
2024
2024
295
302
((R,R)-Whelk-01, 250ꢃ
/
4 mm2, C7H16Á
/
PriOHꢂ
99:1,
/
1 ml minꢁ1, 254 nm, 13b).
6c
6d
Á
/
Á/
2018
2017
2023
2024
2012
2011
300
297
295
294
298
291
6e
2.6. Calculation of the cone angles uR
6f
6g
(Sax)-6h
Cone angles uR of the substituents for compounds 5i
and 5j were determined using published approach [35].
Configurations were taken from the structures obtained
by computer calculations using MM2 method.
6i
(Rax)-6j
6k
Á
/
Á/
292
298
2024
2024
(Sax)-6l
6m
Á
2024
/
Á/
304
(Sax)-6n
(Rax)-6n
2035, 2020 2024, 2012 306 (br)
3. Results and discussion
3.1. Synthesis of the new P,N-ligands
several months and, except 5l and 5m, contain C*-
stereocenters. The new ligands divide into two groups:
The new P,N-hybrid ligands 5aÁ
80Á95% yields by the one-step phosphorylation of
corresponding amino- and imino alcohols:
/n were synthesized in
possessing sp3- (5aÁ
/
g) or sp2-nitrogen atoms (5hÁ
c) and cyclic (5dÁ
/n).
/
The former can bear both acyclic (5aÁ
/
/
g) amino group. The imino groups in the latter ligands
are all of acyclic nature (except 5n, which is a special
case), but the structure of the N-containing part varies
widely. Notably, ligands 5bÁ
/
j and 5lÁn lead to six-
/
membered chelate rings, while 5a and 5k can form
seven-membered chelates. Therefore, the discussed P,N-
ligands possess the identical phosphorus-containing
fragment, but the amino alcohol part varies in the
amino group structure, length of the carbon bridge and
All the ligands 5aÁn are stable in dry conditions for
/

K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á
/
217
211
Table 2
31P-NMR data for complexes 6aÁ
Complex dP (1J(P,Rh), Hz)
atom and about the degree of electronic non-symmetry
of the ligand on the whole [36Á38]).
/n (in CDCl3)
/
6a
6b
6c
139.42 (310.7), 134.10 (303.0)
146.41 (285.4), 144.22 (285.2)
141.24 (283.8), 141.28 (284.6), 140.35 (286.7), 140.31
(286.2), 140.04 (283.9), 139.99 (285.0)
143.60 (288.5), 140.97 (286.4)
6d
6e
6f
The chelate structure of the products is supported by
ES MS data, for in the ES mass spectrum of complex 6i
145.41 (286.7), 145.00 (286.1)
146.72 (287.0), 144.83 (287.4)
146.81 (289.2), 145.37 (289.2)
the peak of [Mꢁ
intensity. The selected spectral data for complexes 6aÁ
are summed up in Tables 1Á
/
Cl]ꢀ cation (m/zꢂ
693) has 100%
/
6g
(Sax)-6h 147.59 (274.7)
/m
6i
147.17 (276.8), 147.05 (276.2)
/3. It should be noted that
(Rax)-6j 145.53 (281.0)
1
a
the values n(CO) and J(P,Rh) for compounds 6aÁ
/
m
6k
147.80 (287.2), 146.41 (289.9)
(Sax)-6l 155.33 (283.6), 148.0 (284.6)
(Tables 1 and 2) exceed the analogous values not only
for the complexes with aminophosphines (by 30Á35
cmꢁ1 and 80Á
100 Hz, respectively) but even for the
complexes with most aminophosphites (by 7Á
10 cmꢁ1
and 10Á15 Hz, respectively [37,38]). This clearly indi-
cates the strong p-acceptor ability of phosphorus centers
in ligands 5aÁm. So, the BINOL block can make two
6m
153.94 (297.9), 150.30 (290.7), 149.82 (292.1)
/
(Sax)-6n 144.67 (275.7)
/
(Rax)-6n 150.26 (262.0), 143.00 (276.7)
/
a
The data were obtained in DMSO-d6.
/
Table 3
13C-NMR data for complexes 6aÁ
/
/b,dÁ/i (in CDCl3)
sufficient contributions into the structure of P,N-hybrid
phosphite ligands, namely, to provide axial chirality and
greatly increase p-acidity of phosphorus atoms. Increas-
ing of the P-center p-acidity in P,N-bidentate ligands is
well known to favour high chemical and optical yields in
Complex
dC (1J(C,Rh) 2J(C,P), Hz)
6a
6b
184.10 (68.9, 19.1), 183.55 (67.5, 19.5)
184.32 (67.9, 18.3), 183.45 (67.8, 18.5)
183.57 (70.2, 15.1), 182.71 (70.2, 16.4)
184.10 (69.5, 19.7), 183.50 (69.4, 19.5)
184.11 (69.7, 18.9), 183.39 (69.9, 18.8)
184.11 (69.5, 19.3), 183.41 (69.2, 19.5)
187.91 (70.6, 17.2)
6d
6e
the allylation, hydroborationÁ/oxidation and hydro-
6f
6g
(Sax)-6h
silylationÁoxidation of alkenes, hydrosilylation of ke-
/
tones processes [39,40].
When designing chiral P,N-bidentate ligands, one
should keep in mind not only the p-acceptor ability of
the phosphorus center but the d-donor ability of the
nitrogen one, as well. Thus, for a series of ferrocene-
based phosphinopyrazoles the optical yields in the Rh-
6i
187.79 (69.7, 18.7), 186.10 (71.4, 17.0)
in number and position of C*-chiral centers. Such a
variability allows to investigate the influence of the
mentioned factors upon complexation and catalytic
properties of the novel P,N-hybride ligands. Most of
the discussed compounds were synthesized from the
cheap racemic BINOL. That allowed us to develop the
methods of synthesis of the ligands and to study their
complexation without using expensive chiral BINOL.
But for catalytic tests a few ligands were obtained from
optically active BINOL. For these compounds an
absolute configuration of the BINOL frame (Sax or
Rax) is shown (see Section 2).
catalyzed hydroborationÁ/oxidation of alkenes [36,41]
and in the Pd-catalyzed hydrosilylationÁ/oxidation of
alkenes [42] were shown to grow with the increasing of
the electron-donor ability of the pyrazole fragment. In
connection with the fact, a concept of electronically non-
symmetric ligands was suggested by Togni and cow-
orkers [36] (the stronger p-acceptor the P-center and d-
donating the N-center are, the more electronically non-
symmetric the compound is). A quantitative estimation
of the parameter is possible by means of n(CO) value in
IR spectrum of the corresponding chlorocarbonyl com-
plex [Rh(CO)Cl(PN)] [36,38]. In particular, for structu-
rally analogous complexes bearing the same phosphorus
and different nitrogen centers, a compound with a
smaller n(CO) value possesses a stronger d-donating
nitrogen-containing center, and, therefore, is more
electronically non-symmetric. From this point of view,
the most electronically non-symmetric ligands among
3.2. Complexation of the new P,N-hybride ligands with
[Rh(CO)2Cl]2
On the base of 5aÁ
/
m chelate chlorocarbonyl Rh(I)
complexes 6aÁm were obtained. n(CO) frequency in the
/
IR spectra and spin-coupling 1J(P,Rh) parameters in the
31P-NMR spectra of such Rh(I) complexes are the
sensitive indicators, which allow to make a conclusion
about electronic properties of the coordinated P,N-
ligands (in particular, about p-acidity of the phosphorus
5aÁn are iminophosphites 5i,h and aminophosphite 5c
/
bearing a distant N-dibenzyl amino group (see Table 1).
The growth of the electron-donating ability of the

212
K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á217
/
nitrogen-containing moiety leads to a decrease in
1J(P,Rh) for 6i,h against 6a,d,g (Table 2).
Notably, complexation of compound 5n proceeds in a
different way. Two optically pure diastereomers ((Sax)-
5n and (Rax)-5n) were specially synthesized from (S)-
and (R)-BINOL and their coordination behavior in-
vestigated. The ES mass spectra of both obtained Rh
complexes showed intensive easily recognizable peaks
Other spectral data for 6aÁ
agreement with their suggested structure. n(RhÃ
frequencies (Table 1) are typical for terminal chlorine
/m are also in good
/Cl)
1
ligands [37]. J(C,Rh) values are in the 68Á75 Hz range
/
(Table 3), which is characteristic for cis-
[Rh(CO)Cl(PfflN)] chelate complexes [37,38]. 2J(C,P)
values (Table 3) prove the cis-position of the carbonyl
and the phosphorus atom [37]. A comparison of 13C-
NMR spectral data for free and coordinated ligands (see
Section 2) reveals marked downfield coordination shifts
of peaks of the carbon atoms neighbor to donor atoms.
[2Mꢁ
/
Cl]ꢀ (m/zꢂ
1307), which clearly indicate the
/
formation of dimer products. Recently, we showed
that insertion of the phosphorus or nitrogen atoms of
P,N-bidentate ligands into cycles can prevent the
ligands from chelation [46]. Most probably, in the case
of complexation of ligands 5n, the dimers are formed
because of similar reasons. Interestingly, ligand (Sax)-5n
gives selectively the product with cis-location of the
nitrogen and phosphorus atoms at Rh, but (Rax)-5n
leads to the mixture of cis- and trans-products:
For example, coordination shifts DdCꢂ
/
dC(complex)ꢁ
/
dC(ligand) for the azomethine carbon atoms of imino-
phosphites 5i,h reach a value of 9 ppm.
The mononuclear structure of metal-complexes 6aÁ
/
m
Such a conclusion was easily made from the 31P-NMR
and IR data for the products of complexation (Tables 1
was additionally proved (in the case of 6d and 6e) by
sedimentation analysis using ultracentrifuge. Measuring
of the diffusion coefficient in DMF gave the diameter of
and 2). Complexes (Sax)-6n (n(CO) 2036 cmꢁ1
1J(P,Rh) 275.7 Hz) and (Rax)-6n (n(CO) 2035 cmꢁ1
,
,
the sphere (14.0 A for 6d and 12.4 A for 6e), in which a
molecule of the complex can be inscribed. This estima-
tion agrees well with the results of a computer calcula-
tion of the molecule structure using MM2 method [43]
1J(P,Rh) 276.7 Hz) have spectral parameters typical for
cis-location of P and N atoms; spectral data for (Rax)-
˚
˚
1
6n? (n(CO) 2020 cmꢁ1, J(P,Rh) 262.0 Hz) are char-
acteristic of trans-structure of the complex [37,47].
˚
˚
(13.9 A for 6d and 13.8 A for 6e). In addition, the
molecular weight of complex 6e has been determined by
Table 4
31P-NMR data for compounds (Rax)-7h, (Rax)-8h, (Rax)-9h, (Sax)-7i,
(Rax)-10j, (Sax)-9l (in CDCl3)
the same method equal to 6329
596).
/
6% (calculated Mrꢂ
/
Compounds 6c,m,l comprise two or more conformers
by six-membered chelate ring (see Table 2) similar to
cationic Rh and Ir complexes with (1R,2R)-
Ph2PCH(Ph)CH(Me)NHMe [44]. In addition, the reac-
tion of 5c with [Rh(CO)2Cl]2 produces some amount of
the trans-[Rh(PfflN)2Cl(CO)] complex, which is char-
acterized by the doublet resonances dP 145.92 (1J(P,Rh)
184.6 Hz) and dP 145.31 (1J(P,Rh) 186.4 Hz) [37,45].
Compound
dP (2J,(P,P?), Hz)
(Rax)-7h
(Rax)-8h
(Rax)-9h
(Sax)-7i
(Rax)-10j
(Sax)-9l
103.20
134.76 (97.2), 50.64 (97.2)
144.80
103.90
139.76
145.26, 144.12

K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á
/
217
213
This remarkable dependence of the products of
complexation structure on the absolute configuration
of the BINOL fragment and on the structure of the
nitrogen-containing fragment must be taken into ac-
count when catalytically applying these ligands.
way. Thus, in the reaction solution of the system 5mÁ
[PdCl2(COD)] (PÁPdꢂ1) in CDCl3 were detected two
conformers of a neutral chelate (dP 113.34, s, 60% and
dP 105.87, s, 25%; n(PdÃ
Cl) 342, 297 cmꢁ1) and a
neutral symmetric complex [Pd(h1-PfflN)2Cl2] (dP
117.00, s, 15%; n(PdÃ
Cl) 322, 306 cmꢁ1) [31,51,52].
When the reaction was performed at the PÁPdꢂ
molar ratio, besides the neutral product [Pd(h1-
PfflN)2Cl2] (24%),
new cationic complex cis-
/
/
/
/
/
/
/
2
3.3. Complexation of the new P,N-hybride ligands with
the Pd(II) precursors
a
[PdCl(h2-PfflN))(h1-PfflN)]ꢀClꢁ (an analogue of
(Rax)-8h) was detected. It consists of two conformers:
(1) dP 63.50, d, 2J(P,P?) 31.8 Hz and dP 123.35, d,
2J(P,P?) 31.8 Hz (60%); (2) dP 64.37, d, 2J(P,P?) 95.7 Hz
and dP 127.80, d, 2J(P,P?) 95.7 Hz (16%). Unfortunately,
Also of great interest and practical importance is the
reaction of the new P,N-ligands with Pd(II) complexes,
for the latter are often used as the catalytic precursors in
the Pd-catalyzed allylic alkylation reactions [13,40]. For
studying of the complexation with Pd(II) were chosen
the attempt to isolate pure cis-[PdCl(h2-PfflN))(h1-
/
aminophosphite 5b and iminophosphites 5hÁj,l,m,
/
/
PfflN)]ꢀBFꢁ4 complex by adding a THF solution of
which gave six-membered Rh chelates selectively and
in high yields (see above). But their reactions with
[PdCl2(COD)] proceed not in the same way. Thus, the
AgBF4 (AgÁ
/
Pdꢂ1) failed. Although the singlet reso-
/
nance dP 117.00 of the neutral [Pd(h1-PfflN)2Cl2] com-
plex vanished from the 31P-NMR spectrum, there
appeared a new set of the quartet signals of AX and
31P-NMR spectrum of the (Rax)-5hÁ
/
[PdCl2(COD)] (PÁ
/
Pdꢂ
/
1) reaction solution contains the signals of the
AB systems in the 47.72Á135.24 ppm range, which
/
neutral chelate complex (Rax)-7h (dP 103.2, s, 60%) and
of the cationic complex (Rax)-8h (AX system: dP 50.64, d
and dP 134.76, d, 2J(P,P?) 97.2 Hz, 40%). When the
reaction was performed at a lower concentration (start-
correspond to various cationic complexes of unknown
structures [49,50].
Ligand 5b does not produce cationic complexes when
reacting with [PdCl2(COD)]. Thus, at the PÁ
/
Pdꢂ1
/
ing with 0.5ꢃ
/
10ꢁ4 mol of [PdCl2(COD)] instead of 1ꢃ
/
molar ratio, the reaction solution gives in the 31P-
NMR spectrum peaks at dP 90.63, 77.44 and 50.76
ppm. Their characteristic chemical shifts allowed to
ascribe them to the complexes [Pd(h1-PfflN)2Cl2],
[Pd(h2-PfflN)Cl2] [19,27] and [Pd2Cl2(m-Cl)2(h1-PfflN)2]
[53,54], correspondingly. Indeed, when the reaction was
10ꢁ4 mol), the share of the (Rax)-7h product grew (up to
72%), as expected. Complex (Rax)-7h was obtained in a
pure state by the reaction of (Rax)-5h with
[PdCl2(CH3CN)2] (PÁ
was synthesized by the reaction of (Rax)-5h with
[PdCl2(CH3CN)2] (PÁPdꢂ2) or with [PdCl2(COD)]
(PÁPdꢂ2). Both complexes were fully characterized
/
Pdꢂ
1); pure complex (Rax)-8h
/
/
/
performed at the PÁ
/
Pdꢂ2 molar ratio, the only
/
/
/
broaden singlet dP 90.63 was observed.
by the usual spectral methods (see Section 2 and Table
4). Thus, the cis-positioning of the phosphorus atoms in
complex (Rax)-8h is proved by the characteristic value of
In general, complexation of the new BINOL-based
P,N-hybride phosphites with [PdCl2(COD)] proceed not
selectively. That must be taken into account when
choosing starting metal precursors for catalytic reac-
tions. On the other hand, using [PdCl2(CH3CN)2] and
[Pd(allyl)Cl]2 leads to the neutral and cationic Pd
chelates selectively and in high yields. The selective
synthesis of complex (Rax)-7h has been already described
(see above). Its homologue (Sax)-7i was obtained in a
similar way:
the 2J(P,P?) parameter (97.2 Hz) and the only n(PdÃ
/
Cl)
band (298 cmꢁ1, CsI, Nujol) in its IR spectrum [15,48Á
/
50]. The results of cyclic voltammetry for the (Rax)-8h
solution in DCM reveal the presence of Clꢁ anions in its
structure (Ena
ꢂ
/
ꢀ1.3 eV), for the peak grows upon
/
adding of [Et3NBz]ꢀClꢁ into the solution. In general,
complexation of ligand (Rax)-5h can be illustrated with
the scheme:
The complex was characterized by usual spectral
methods (see Section 2 and Table 4). It is notable that
the n(PdÃ
(Sax)-7i, (Rax)-7h and (Rax)-8h have maximums at about
300 cmꢁ1, which is characteristic of the PdÃ
Cl bonds
/
Cl) adsorption bands in the IR spectra of
/
trans-positioned to the BINOL-derived phosphite group
[31]. Therefore, the trans-influence of the latter is lower
in comparison with other phosphites, for which the
Iminophosphite 5m undergoes complexation in a similar

214
K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á217
/
Table 5
Enantioselective allylic alkylation of 3-penten-2-yl ethyl carbonate
(Rax)-10j either because of the fast interconversion of the
isomers or because of the absence of one of the isomers
(see [40] and references cited therein, [56,57]).
with dimethyl malonate according to Scheme 1 (L*Á
/
Pdꢂ2)
a
b
Entry L*
Solvent
T (8C)
Yield (%)
% ee
1
2
(Rax)-5a
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
DCM
Toluene
CH3CN
THF
THF
THF
DCM
THF
THF
THF
THF
DCM
THF
THF
THF
DCM
Toluene
THF
THF
THF
r.t.
ꢁ18
r.t.
5
30
3
2 (S)
(Rax)-5a
(Rax)-5b
(Rax)-5b
(Rax)-5b
(Sax)-5h
(Sax)-5h
(Sax)-5h
(Sax)-5h
(Sax)-5h
(Sax)-5h
(Sax)-5h
(Sax)-5h
(Sax)-5h
(Rax)-5h
(Rax)-5h
(Rax)-5h
(Rax)-5h
(Sax)-5i
(Sax)-5i
(Rax)-5i
(Sax)-5j
(Sax)-5j
(Rax)-5j
(Rax)-5j
(Rax)-5j
(Rax)-5j
(Rax)-5j
(Sax)-5l
(Rax)-5n
11
34 (S)
26 (R)
21 (R)
18 (R)
2 (S)
3
50
45
30
60
80
30
90
70
70
85
0
4
5
ꢁ18
65
6
c
Scheme 1.
7
r.t.
r.t.
r.t.
5
46 (S)
9 (S)
d
8
9
58 (S)
43 (S)
35 (S)
4 (S)
3.4. Pd-catalyzed allylic substitution reactions
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
ꢁ20
r.t.
r.t.
r.t.
r.t.
5
Several of the new P,N-ligands based on optically
active BINOLs were tested in the Pd-catalyzed allylic
alkylation of 3-penten-2-yl carbonate with dimethyl
Á/
Á/
0
95
65
65
0
5 (S)
11 (S)
3 (S)
malonate (Scheme 1, Rꢂ
/
Et, baseꢂBSA, KOAc).
/
The obtained results are summed up in Table 5. The
following conclusions can be made from them: (1) the
ꢁ20
r.t.
r.t.
ꢁ18
r.t.
r.t.
r.t.
r.t.
r.t.
5
Á/
derivatives of the well-known chiral inductorsÁaminoal-
/
90
55
95
65
98
25
55
86
93
80
20
40
20
41 (R)
39 (R)
48 (R)
50 (R)
49 (R)
74 (R)
76 (R)
81 (R)
19 (R)
81 (R)
7 (S)
cohols Chirald ((Rax)-5a) and N-methylephedrine
((Rax)-5b) gave poor results (less than 34% ee), as well
as oxazolinephosphite (Rax)-5n (entry 30); (2) the best
results were shown by ligands bearing imino groups*
/
(Sax)-5h and (Rax)-5j (up to 81% ee). The C*-stereo-
centers in the nitrogen-containing fragments are crucial,
for ligand (Sax)-5l, which does not have one, gave only
c
r.t.
r.t.
r.t.
r.t.
r.t.
7% ee (entry 29). Notably, ligands 2aÁd, which, similar
/
to (Sax)-5l, are only of axial chirality, also shown low
enantioselectivity (see Section 1); (3) presence of a
nitrogen donor atom is crucial, because the previously
obtained by us P-monodentate
28 (R)
7 (S)
a
Yield of analytically pure product after column chromatography.
The enantiomeric excesses were determined by chiral GC (fused
b
silica capillary column DP-TFA-g-CD, 90 8C, He, 1.8 bar).
c
L*Á
L*ÁPdꢂ4.
/
Pdꢂ1.
d
/
n(PdÃ
/
Cl) bands are normally observed at 280Á290
/
cmꢁ1 [19,27,46,55].
Reactions of [Pd(allyl)Cl]2 with ligands (Rax)-5h,
(Rax)-5j and (Sax)-5l lead to cationic chelate complexes
(Rax)-9h, (Rax)-10j and (Sax)-9l (complex 10j was
obtained by the ion exchange reaction with AgBF4):
phosphite (11) [58] is ineffective (entry 31); (4) the
optical yields are strongly dependent on the optical
configuration of the BINOL fragment (compare entries
9 and 15, 23 and 27) and, sometimes, on the solvent used
(compare, for example, entries 9 and 12); (5) changing of
the L*Á
catalytic results (compare entries 24 and 25), but if the
ratio is increased up to L*ÁPdꢂ4, the results become
/
Pd ratio from 2 to 1 slightly improves the
The products were characterized by the standard
physical methods (see Section 2 and Table 4) and, in
addition, complex (Rax)-9h was analyzed by cyclic
/
/
much worse (compare entries 7 and 8).
It must be noted that ligands (Sax)-5j and (Rax)-5j
gave generally higher results than very similar to them
ligands (Sax)-5i and (Rax)-5i. The electronic properties
(including a degree of electronic non-symmetry) of
ligands 5i and 5j are very close, since the values of the
voltammetry (in CH3OH, Ena
ꢂ
/
ꢀ1.29 eV). It should
/
be noted that there are two sets of peaks in the 31P- and
13C-NMR spectra of (Sax)-9l, which indicates the
existence of the exo- and endo-isomers of the com-
pound. It is not observed for complexes (Rax)-9h and
1
n(CO) and J(P,Rh) parameters in their corresponding

K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á
/
217
215
Table 6
Enantioselective hydrosilylation of ketones 12a,b (see Scheme 2
MꢂRh)
The matter is that 1,3-dimethyl-substituted allyl sub-
strates are referred to as unmanageable ones [59] and it
is rather difficult to reach high stereoselectivity in that
case. To the best of our knowledge, only two P,N-
hybrid ligands gave in the mentioned above allylation
process an enantioselectivity higher than 80%: one of the
a
Entry L*
Ketone
L*Á/M
Yield (%)
% ee
1
2
(Rax)-5a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
12b
12b
12b
12a
12a
12a
12a
12a
12a
12a
12a
12a
12a
1
2
1
2
1
2
1
2
1
2
3
1
2
3
1
2
1
2
3
4
1
2
3
1
2
3
1
2
1
2
3
1
2
3
1
2
60
65
54
73
44
56
57
61
3
19 (R)
17 (S)
8 (R)
13 (R)
10 (R)
15 (R)
19 (S)
23 (S)
11 (R)
20 (S)
16 (S)
0
(Rax)-5a
(Sax)-5h
(Sax)-5h
(Sax)-5i
(Sax)-5i
(Rax)-5i
(Rax)-5i
(Rax)-5j
(Rax)-5j
(Rax)-5j
(Sax)-5j
(Sax)-5j
(Sax)-5j
(Sax)-5l
(Sax)-5l
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Rax)-5n
(Sax)-5n
(Sax)-5n
(Sax)-5n
(Sax)-5n
(Sax)-5n
11
new generation phosphinooxazolines (70Á
/
90% ee) [33]
and a 2-(phosphinoaryl)pyridine derived ligand (Scheme
3
4
i
5
1, Rꢂ
results were achieved by thorough optimization of the
reaction conditions at a low temperature (ꢁ25Á
/
Me, Pr, Ph, 78Á93% ee) [59]. And these high
/
6
7
/
/
ꢁ
/
8
9
40 8C) and, in the latter case, by addition of crown
ethers. So, compound (Rax)-5j holds a worthy of note
position, surpassing many well-known P,N-bidentate
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
19
20
43
13
11
45
11
58
30
74
1
ligands [60Á62].
/
1 (R)
1 (R)
2 (R)
3 (R)
18 (S)
43 (S)
58 (S)
19 (S)
11 (S)
38 (S)
5 (R)
2
b
b
b
97
49
1
Scheme 2.
90
35
40
64
69
91
24
1
3.5. Rh-catalyzed hydrosilylation reactions
55
60
Some of the new P,N-hybride phosphites were also
tested in the asymmetric reduction of prochiral ketones
with diphenylsilane (Scheme 2).
The obtained results are summed up in Table 6. As in
the Pd-catalyzed allylation, ligands (Rax)-5a, (Sax)-5l
1 (R)
4 (R)
8 (R)
14 (R)
2 (R)
7 (S)
16 (S)
21 (S)
0
b
b
b
69
73
56
78
96
and 11 are not effective (entries 1Á
Rather low results were also shown by iminophosphites
14). The best results were obtained with
/
2, 15Á
/
16, 32Á36).
/
11
11
b
11
11
(entries 3Á
/
b
ligand (Rax)-5n (up to 58% ee for 13a and up to 60%
ee for 13b), the absolute configuration of the BINOL
fragment being a crucial factor for the optical yields
(compare with the results given by (Sax)-5n, Table 6).
3 (S)
a
The yield of 13a after distillation and 13b after purification [34].
[Ir(COD)Cl]2 was used as a catalyst precursor.
b
[Rh(CO)Cl(PfflN)] complexes are almost the same
(Tables 1 and 2). So, it is the steric properties of the
ligands 5i and 5j what is responsible for the difference in
their enantioselectivity. Ligands 5i and 5j are of similar
The L*ÁM ratio and solvent also deeply influence the
/
catalytic results (Table 6).
Despite some known P,N-bidentate ligands give more
than 90% ee in the reaction (see [13,40] and references
cited therein), the obtained results hold a worthy of note
position. Especially important is obtaining of enantio-
merically enriched 1-ferrocenylethanol (13b), which is a
valuable chiral synthon in the synthesis of some anti-
cancer drugs [63]. Besides, the 31P-NMR spectral
structures and only Ã
/
NÄ/CHR fragments are different.
To estimate the bulkiness of the substituents, the cone
angles uR for the p-C6H4NMe2 and Cp2Fe fragments
have been calculated mathematically by constructing the
corresponding computer models. The calculated cone
monitoring of the [Rh(COD)Cl]2Á
mixture (in d8-toluene) revealed the presence of several
complex products. Thus, when the L*ÁRh ratio varied
in the 1Á3 range, a set of doublet signals dP 128.94Á
156.83 (1J(P,Rh) 259.3Á
311.0 Hz) were detected. So, it
/
(Rax)-5n reaction
angle for the Cp2Fe fragment (uRꢂ
larger then the angle for the p-C6H4NMe2 fragment
(uRꢂ133). Hence, bulky substituents attached to the
/
159) is significantly
/
/
imine group of the P,N-iminophosphite ligands are
likely to lead to higher optical yields in the catalytic
reaction.
It should be noted that the catalytic system based on
(Rax)-5j allows reaching a very high enantioselectivity.
/
/
/
is an actual task to prepare a real catalyst selectively,
free of the by-products of complexation. Such experi-
ments are in progress in our group.

216
K.N. Gavrilov et al. / Journal of Organometallic Chemistry 655 (2002) 204Á217
/
[10] A.H.M. de Vries, A. Metsma, B.L. Feringa, Angew. Chem. Int.
Ed. Engl. 35 (1996) 2374.
4. Conclusion
[11] K. Selvakumar, M. Valentini, P.S. Prigosin, A. Albinati, Orgno-
metallics 18 (1999) 4591.
A series of novel chiral P,N-hybrid phosphite ligands
was prepared. They bear the identical BINOL-derived
phosphorus fragment and widely vary in the structure of
the amino alcohol part. Most of the ligands react with
[Rh(CO)2Cl]2 highly selectively giving stable chelate
complexes [Rh(CO)Cl(PfflN)]. The only exception is
phosphitooxazoline (5n), which leads to the dimeric
product [Rh(CO)Cl(PfflN)]2 of the ‘head-to-tail’ type. In
contrast, complexation with [PdCl2(COD)] gives mix-
tures of the chelates [PdCl2(PfflN)] and products con-
taining two coordinated ligand molecules: cis-
[12] G. Helmchen, A. Pfaltz, Acc. Chem. Res. 33 (2000) 336.
[13] F. Fache, E. Schultz, M.L. Tommasino, M. Lemaire, Chem. Rev.
100 (2000) 2159.
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The authors gratefully acknowledge receiving quin-
coridine from Buchler GmbH (Germany), chiral HPLC
columns from Regis Technologies Inc. (USA) and thank
Dr M.M. Il’in (Institute of Organoelement Compounds,
Moscow) for his assistance in characterizing the pro-
ducts. This work was partially supported by the Russian
Foundation for Basic Research (Grants No. 00-15-
99341 and 00-15-97427).
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