Origin of the chemical stability of phosphine-phospho­ramidites: structural study of an UPPhos-type crystal and application of UPPhos in the asymmetric hydrogenation of imines

Balogh, S.; Farkas, G.; Holczbauer, T.; Bakos, J.

doi:10.1107/S2053229617010403

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Origin of the chemical stability of phosphine-phosphoramidites: structural study of an UPPhos-type crystal and application of UPPhos in the asymmetric hydrogenation of imines

S. Balogh, G. Farkas, T. Holczbauer and J. Bakos

Phosphine–phosphoramidites (PPAs) are heterobidentate ligands that have been developed in the last two decades and have been used successfully in asymmetric catalytic reactions. A single crystal of the PPA (11bS)-N-[(2S,4S)-4-(diphenylphosphanyl)pentan-2-yl]-N-methyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine, C₃₈H₃₅NO₂P₂, was prepared and structurally characterized by single-crystal X-ray diffraction and density functional theory (DFT) calculations. Structure elucidation revealed unique features which might have a significant effect in the excellent chemical stability of this type of molecule. The conformation of the molecule provides an optimal chelating structure. Iridium complexes of UPPhos were found to be efficient catalysts in the asymmetric hydrogenation of imines {UPPhos is (11bS)-N-[(2S,4S)-4-(diphenylphosphanyl)pentan-2-yl]-N-(propan-2-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine}.

Keywords: phosphine–phosphoramidite; through-space coupling; PPA; iridium-catalyzed hydrogenation; crystal structure; computational chemistry; DFT; asymmetric catalytic reaction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617010403/sk3658sup1.cif Contains datablocks I, global
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup10.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup11.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup12.cdx Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229617010403/sk3658Isup2.hkl Contains datablock I
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup3.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup4.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup5.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup6.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup7.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup8.cdx Supplementary material
	Chemdraw file https://doi.org/10.1107/S2053229617010403/sk3658Isup9.cdx Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229617010403/sk3658sup13.pdf Additional figures and tables

CCDC reference: 1562039

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008; data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

(11bS)-N-[(2S,4S)-4-(Diphenylphosphanyl)pentan-2-yl]-N-methyldinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine top

Crystal data top

C₃₈H₃₅NO₂P₂	F(000) = 632
M_r = 599.61	D_x = 1.233 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71075 Å
a = 11.7931 (5) Å	Cell parameters from 30659 reflections
b = 10.4209 (5) Å	θ = 3.1–25.4°
c = 14.0792 (6) Å	µ = 0.17 mm⁻¹
β = 111.0806 (10)°	T = 294 K
V = 1614.46 (12) Å³	Block, colourless
Z = 2	0.69 × 0.38 × 0.31 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	5701 independent reflections
Radiation source: NORMAL-focus sealed tube	4190 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 10.0000 pixels mm^-1	θ_max = 25.0°, θ_min = 3.1°
dtprofit.ref scans	h = −14→14
Absorption correction: numerical (NUMABS; Higashi, 2002)	k = −12→12
T_min = 0.891, T_max = 0.964	l = −16→16
46478 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0341P)² + 0.2524P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
5701 reflections	Δρ_max = 0.12 e Å⁻³
391 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1519 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (3)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.37367 (10)	0.14510 (13)	0.15122 (9)	0.0825 (4)
P2	0.08243 (10)	0.11423 (11)	−0.09799 (8)	0.0730 (3)
O1	0.4582 (3)	0.1941 (3)	0.2686 (2)	0.0929 (10)
O1'	0.4674 (2)	0.0328 (3)	0.1377 (2)	0.0769 (8)
N1	0.3925 (3)	0.2482 (4)	0.0701 (2)	0.0818 (11)
C1	0.6467 (4)	0.0826 (4)	0.3268 (3)	0.0651 (10)
C2	0.5852 (5)	0.1957 (5)	0.3081 (3)	0.0797 (13)
C3	0.6442 (7)	0.3165 (5)	0.3333 (4)	0.0979 (17)
H3	0.5993	0.3919	0.3237	0.127*
C4	0.7674 (7)	0.3194 (6)	0.3716 (4)	0.1070 (18)
H4	0.8063	0.3982	0.3892	0.139*
C5	0.9688 (6)	0.2116 (6)	0.4204 (4)	0.1044 (17)
H5	1.0095	0.2894	0.4381	0.136*
C6	1.0327 (5)	0.1025 (8)	0.4277 (4)	0.1142 (17)
H6	1.1171	0.1054	0.4503	0.148*
C7	0.9733 (5)	−0.0132 (6)	0.4015 (4)	0.0969 (15)
H7	1.0182	−0.0875	0.4050	0.126*
C8	0.8507 (4)	−0.0210 (5)	0.3707 (3)	0.0751 (12)
H8	0.8136	−0.1010	0.3550	0.098*
C9	0.7779 (4)	0.0888 (4)	0.3618 (3)	0.0688 (11)
C10	0.8380 (5)	0.2091 (5)	0.3857 (3)	0.0858 (13)
C1'	0.5800 (4)	−0.0414 (4)	0.3057 (3)	0.0621 (10)
C2'	0.4943 (4)	−0.0639 (4)	0.2117 (3)	0.0688 (11)
C3'	0.4306 (4)	−0.1801 (5)	0.1847 (3)	0.0827 (13)
H3'	0.3752	−0.1925	0.1190	0.108*
C4'	0.4507 (4)	−0.2744 (5)	0.2555 (4)	0.0858 (13)
H4'	0.4101	−0.3522	0.2373	0.112*
C5'	0.5447 (5)	−0.3489 (5)	0.4330 (4)	0.0912 (14)
H5'	0.5041	−0.4269	0.4161	0.119*
C6'	0.6151 (5)	−0.3247 (5)	0.5305 (4)	0.0974 (16)
H6'	0.6215	−0.3856	0.5805	0.127*
C7'	0.6784 (5)	−0.2093 (5)	0.5571 (4)	0.0906 (14)
H7'	0.7271	−0.1944	0.6246	0.118*
C8'	0.6699 (4)	−0.1178 (4)	0.4854 (3)	0.0769 (12)
H8'	0.7127	−0.0413	0.5046	0.100*
C9'	0.5966 (4)	−0.1380 (4)	0.3822 (3)	0.0635 (10)
C10'	0.5320 (4)	−0.2562 (4)	0.3561 (3)	0.0728 (11)
C11	0.2862 (4)	0.3289 (4)	0.0130 (3)	0.0746 (11)
H11	0.2188	0.3021	0.0337	0.097*
C12	0.5068 (4)	0.2723 (7)	0.0550 (4)	0.121 (2)
H12A	0.5711	0.2257	0.1049	0.169*
H12B	0.5247	0.3624	0.0619	0.169*
H12C	0.4999	0.2446	−0.0119	0.169*
C13	0.3086 (6)	0.4711 (5)	0.0388 (4)	0.1202 (19)
H13A	0.2347	0.5181	0.0065	0.168*
H13B	0.3702	0.5022	0.0148	0.168*
H13C	0.3351	0.4823	0.1112	0.168*
C14	0.2467 (4)	0.3059 (4)	−0.1013 (3)	0.0728 (11)
H14A	0.3120	0.3322	−0.1236	0.095*
H4B	0.1769	0.3597	−0.1359	0.095*
C15	0.2136 (4)	0.1663 (4)	−0.1336 (3)	0.0714 (11)
H15	0.2833	0.1140	−0.0932	0.093*
C16	0.1984 (4)	0.1465 (5)	−0.2459 (3)	0.0882 (13)
H16A	0.2728	0.1685	−0.2551	0.123*
H16B	0.1340	0.2003	−0.2882	0.123*
H16C	0.1790	0.0583	−0.2642	0.123*
C1P	0.0657 (4)	−0.0558 (4)	−0.1324 (3)	0.0666 (10)
C2P	−0.0460 (4)	−0.1160 (5)	−0.1539 (3)	0.0797 (12)
H2P	−0.1138	−0.0671	−0.1583	0.104*
C3P	−0.0582 (4)	−0.2473 (5)	−0.1688 (4)	0.0890 (13)
H3P	−0.1339	−0.2852	−0.1831	0.116*
C4P	0.0398 (5)	−0.3223 (5)	−0.1628 (4)	0.0915 (13)
H4P	0.0315	−0.4106	−0.1724	0.119*
C5P	0.1499 (4)	−0.2642 (5)	−0.1424 (4)	0.0953 (15)
H5P	0.2170	−0.3137	−0.1389	0.124*
C6P	0.1636 (4)	−0.1328 (4)	−0.1268 (4)	0.0843 (13)
H6P	0.2397	−0.0958	−0.1123	0.110*
C7P	−0.0452 (4)	0.1921 (4)	−0.1969 (3)	0.0719 (11)
C8P	−0.1039 (4)	0.1486 (4)	−0.2964 (3)	0.0765 (11)
H8P	−0.0806	0.0708	−0.3161	0.099*
C9P	−0.1958 (4)	0.2184 (5)	−0.3661 (4)	0.0871 (13)
H9P	−0.2345	0.1865	−0.4315	0.113*
C10P	−0.2303 (5)	0.3336 (6)	−0.3399 (6)	0.1047 (17)
H10P	−0.2917	0.3806	−0.3876	0.136*
C11P	−0.1751 (5)	0.3802 (5)	−0.2436 (6)	0.1059 (19)
H11P	−0.1983	0.4594	−0.2260	0.138*
C12P	−0.0847 (4)	0.3099 (5)	−0.1723 (4)	0.0916 (15)
H12P	−0.0494	0.3415	−0.1064	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0706 (7)	0.1052 (10)	0.0784 (7)	0.0213 (7)	0.0350 (6)	0.0316 (7)
P2	0.0754 (7)	0.0761 (8)	0.0708 (6)	−0.0117 (6)	0.0304 (5)	−0.0040 (6)
O1	0.113 (2)	0.111 (3)	0.0624 (16)	0.050 (2)	0.0400 (17)	0.0167 (16)
O1'	0.0694 (17)	0.101 (2)	0.0620 (16)	0.0202 (16)	0.0262 (14)	0.0090 (16)
N1	0.055 (2)	0.113 (3)	0.074 (2)	−0.004 (2)	0.0197 (17)	0.032 (2)
C1	0.082 (3)	0.061 (3)	0.052 (2)	0.007 (2)	0.024 (2)	0.0032 (18)
C2	0.099 (4)	0.081 (4)	0.057 (2)	0.026 (3)	0.026 (2)	0.006 (2)
C3	0.160 (6)	0.062 (3)	0.075 (3)	0.025 (4)	0.046 (4)	0.007 (3)
C4	0.155 (6)	0.082 (4)	0.082 (3)	−0.023 (4)	0.041 (4)	−0.001 (3)
C5	0.106 (4)	0.112 (5)	0.090 (4)	−0.046 (4)	0.030 (3)	−0.006 (3)
C6	0.090 (4)	0.136 (5)	0.111 (4)	−0.014 (5)	0.030 (3)	0.003 (4)
C7	0.075 (3)	0.116 (5)	0.097 (4)	−0.002 (3)	0.028 (3)	0.004 (3)
C8	0.069 (3)	0.081 (3)	0.074 (3)	0.000 (2)	0.024 (2)	−0.001 (2)
C9	0.080 (3)	0.065 (3)	0.060 (2)	−0.007 (2)	0.024 (2)	0.000 (2)
C10	0.116 (4)	0.072 (3)	0.071 (3)	−0.004 (3)	0.035 (3)	0.003 (2)
C1'	0.064 (2)	0.064 (3)	0.061 (2)	0.010 (2)	0.026 (2)	0.002 (2)
C2'	0.065 (3)	0.082 (3)	0.064 (3)	0.012 (2)	0.029 (2)	0.001 (2)
C3'	0.071 (3)	0.108 (4)	0.071 (3)	−0.005 (3)	0.027 (2)	−0.021 (3)
C4'	0.089 (3)	0.081 (3)	0.099 (4)	−0.017 (3)	0.047 (3)	−0.023 (3)
C5'	0.114 (4)	0.063 (3)	0.121 (4)	0.005 (3)	0.072 (3)	0.009 (3)
C6'	0.129 (4)	0.079 (4)	0.104 (4)	0.029 (3)	0.066 (4)	0.028 (3)
C7'	0.114 (4)	0.086 (4)	0.075 (3)	0.019 (3)	0.037 (3)	0.016 (3)
C8'	0.088 (3)	0.073 (3)	0.068 (3)	0.012 (2)	0.026 (2)	0.005 (2)
C9'	0.068 (3)	0.059 (3)	0.070 (3)	0.008 (2)	0.032 (2)	0.000 (2)
C10'	0.079 (3)	0.066 (3)	0.084 (3)	0.008 (2)	0.042 (3)	−0.006 (2)
C11	0.066 (3)	0.075 (3)	0.074 (3)	−0.006 (2)	0.014 (2)	0.012 (2)
C12	0.060 (3)	0.198 (6)	0.108 (4)	−0.009 (3)	0.034 (3)	0.054 (4)
C13	0.156 (5)	0.081 (4)	0.105 (4)	−0.030 (4)	0.025 (4)	−0.008 (3)
C14	0.067 (3)	0.069 (3)	0.072 (3)	−0.008 (2)	0.012 (2)	0.015 (2)
C15	0.068 (2)	0.069 (3)	0.075 (3)	−0.001 (2)	0.023 (2)	0.009 (2)
C16	0.101 (3)	0.088 (3)	0.090 (3)	−0.016 (3)	0.052 (2)	−0.008 (3)
C1P	0.067 (3)	0.068 (3)	0.064 (2)	−0.005 (2)	0.022 (2)	0.012 (2)
C2P	0.068 (3)	0.084 (3)	0.092 (3)	−0.005 (2)	0.033 (2)	0.009 (2)
C3P	0.078 (3)	0.083 (4)	0.102 (3)	−0.021 (3)	0.028 (3)	0.013 (3)
C4P	0.090 (3)	0.073 (3)	0.108 (3)	−0.007 (3)	0.031 (3)	0.016 (3)
C5P	0.079 (3)	0.076 (4)	0.129 (4)	0.009 (3)	0.036 (3)	0.018 (3)
C6P	0.068 (3)	0.070 (3)	0.108 (4)	−0.001 (2)	0.022 (3)	0.017 (3)
C7P	0.069 (3)	0.066 (3)	0.089 (3)	−0.004 (2)	0.039 (2)	−0.004 (2)
C8P	0.081 (3)	0.067 (3)	0.082 (3)	0.008 (2)	0.030 (2)	0.006 (2)
C9P	0.080 (3)	0.079 (3)	0.097 (3)	−0.003 (3)	0.025 (3)	0.015 (3)
C10P	0.078 (3)	0.076 (4)	0.161 (6)	−0.001 (3)	0.045 (4)	0.013 (4)
C11P	0.078 (3)	0.062 (3)	0.197 (7)	0.004 (3)	0.073 (4)	−0.011 (4)
C12P	0.078 (3)	0.073 (3)	0.135 (4)	−0.010 (3)	0.053 (3)	−0.029 (3)

Geometric parameters (Å, º) top

P1—N1	1.641 (3)	C8'—C9'	1.414 (5)
P1—O1'	1.667 (3)	C8'—H8'	0.9300
P1—O1	1.673 (3)	C9'—C10'	1.425 (6)
P2—C1P	1.829 (4)	C11—C14	1.525 (6)
P2—C7P	1.831 (4)	C11—C13	1.526 (6)
P2—C15	1.870 (4)	C11—H11	0.9800
O1—C2	1.398 (5)	C12—H12A	0.9600
O1'—C2'	1.401 (5)	C12—H12B	0.9600
N1—C12	1.461 (5)	C12—H12C	0.9600
N1—C11	1.483 (5)	C13—H13A	0.9600
C1—C2	1.360 (6)	C13—H13B	0.9600
C1—C9	1.446 (6)	C13—H13C	0.9600
C1—C1'	1.486 (6)	C14—C15	1.532 (6)
C2—C3	1.420 (7)	C14—H14A	0.9700
C3—C4	1.357 (8)	C14—H4B	0.9700
C3—H3	0.9300	C15—C16	1.539 (5)
C4—C10	1.391 (8)	C15—H15	0.9800
C4—H4	0.9300	C16—H16A	0.9600
C5—C6	1.348 (8)	C16—H16B	0.9600
C5—C10	1.440 (8)	C16—H16C	0.9600
C5—H5	0.9300	C1P—C6P	1.384 (6)
C6—C7	1.376 (8)	C1P—C2P	1.391 (5)
C6—H6	0.9300	C2P—C3P	1.384 (6)
C7—C8	1.354 (6)	C2P—H2P	0.9300
C7—H7	0.9300	C3P—C4P	1.372 (6)
C8—C9	1.409 (6)	C3P—H3P	0.9300
C8—H8	0.9300	C4P—C5P	1.366 (6)
C9—C10	1.420 (6)	C4P—H4P	0.9300
C1'—C2'	1.366 (5)	C5P—C6P	1.387 (6)
C1'—C9'	1.436 (5)	C5P—H5P	0.9300
C2'—C3'	1.404 (6)	C6P—H6P	0.9300
C3'—C4'	1.358 (6)	C7P—C8P	1.397 (5)
C3'—H3'	0.9300	C7P—C12P	1.401 (6)
C4'—C10'	1.408 (6)	C8P—C9P	1.378 (6)
C4'—H4'	0.9300	C8P—H8P	0.9300
C5'—C6'	1.348 (7)	C9P—C10P	1.361 (7)
C5'—C10'	1.419 (6)	C9P—H9P	0.9300
C5'—H5'	0.9300	C10P—C11P	1.365 (8)
C6'—C7'	1.394 (7)	C10P—H10P	0.9300
C6'—H6'	0.9300	C11P—C12P	1.383 (7)
C7'—C8'	1.366 (6)	C11P—H11P	0.9300
C7'—H7'	0.9300	C12P—H12P	0.9300

N1—P1—O1'	96.82 (16)	N1—C11—C13	112.4 (4)
N1—P1—O1	107.84 (19)	C14—C11—C13	111.4 (4)
O1'—P1—O1	98.21 (15)	N1—C11—H11	107.2
C1P—P2—C7P	104.29 (19)	C14—C11—H11	107.2
C1P—P2—C15	103.35 (19)	C13—C11—H11	107.2
C7P—P2—C15	101.54 (18)	N1—C12—H12A	109.5
C2—O1—P1	124.7 (2)	N1—C12—H12B	109.5
C2'—O1'—P1	113.7 (2)	H12A—C12—H12B	109.5
C12—N1—C11	118.0 (3)	N1—C12—H12C	109.5
C12—N1—P1	125.3 (3)	H12A—C12—H12C	109.5
C11—N1—P1	116.7 (2)	H12B—C12—H12C	109.5
C2—C1—C9	117.3 (4)	C11—C13—H13A	109.5
C2—C1—C1'	120.5 (4)	C11—C13—H13B	109.5
C9—C1—C1'	122.2 (3)	H13A—C13—H13B	109.5
C1—C2—O1	119.2 (5)	C11—C13—H13C	109.5
C1—C2—C3	122.7 (5)	H13A—C13—H13C	109.5
O1—C2—C3	117.9 (5)	H13B—C13—H13C	109.5
C4—C3—C2	118.5 (5)	C11—C14—C15	114.3 (3)
C4—C3—H3	120.7	C11—C14—H14A	108.7
C2—C3—H3	120.7	C15—C14—H14A	108.7
C3—C4—C10	122.6 (5)	C11—C14—H4B	108.7
C3—C4—H4	118.7	C15—C14—H4B	108.7
C10—C4—H4	118.7	H14A—C14—H4B	107.6
C6—C5—C10	120.8 (5)	C14—C15—C16	110.8 (3)
C6—C5—H5	119.6	C14—C15—P2	110.1 (3)
C10—C5—H5	119.6	C16—C15—P2	115.8 (3)
C5—C6—C7	120.1 (5)	C14—C15—H15	106.5
C5—C6—H6	120.0	C16—C15—H15	106.5
C7—C6—H6	120.0	P2—C15—H15	106.5
C8—C7—C6	121.4 (5)	C15—C16—H16A	109.5
C8—C7—H7	119.3	C15—C16—H16B	109.5
C6—C7—H7	119.3	H16A—C16—H16B	109.5
C7—C8—C9	121.7 (5)	C15—C16—H16C	109.5
C7—C8—H8	119.1	H16A—C16—H16C	109.5
C9—C8—H8	119.1	H16B—C16—H16C	109.5
C8—C9—C10	117.3 (4)	C6P—C1P—C2P	117.1 (4)
C8—C9—C1	122.4 (4)	C6P—C1P—P2	122.6 (3)
C10—C9—C1	120.2 (4)	C2P—C1P—P2	119.9 (4)
C4—C10—C9	118.2 (5)	C3P—C2P—C1P	121.1 (4)
C4—C10—C5	123.1 (6)	C3P—C2P—H2P	119.4
C9—C10—C5	118.6 (5)	C1P—C2P—H2P	119.4
C2'—C1'—C9'	117.4 (4)	C4P—C3P—C2P	121.0 (4)
C2'—C1'—C1	119.8 (4)	C4P—C3P—H3P	119.5
C9'—C1'—C1	122.7 (3)	C2P—C3P—H3P	119.5
C1'—C2'—O1'	119.2 (4)	C5P—C4P—C3P	118.4 (5)
C1'—C2'—C3'	123.2 (4)	C5P—C4P—H4P	120.8
O1'—C2'—C3'	117.6 (4)	C3P—C4P—H4P	120.8
C4'—C3'—C2'	119.4 (4)	C4P—C5P—C6P	121.2 (5)
C4'—C3'—H3'	120.3	C4P—C5P—H5P	119.4
C2'—C3'—H3'	120.3	C6P—C5P—H5P	119.4
C3'—C4'—C10'	121.1 (4)	C1P—C6P—C5P	121.1 (4)
C3'—C4'—H4'	119.5	C1P—C6P—H6P	119.4
C10'—C4'—H4'	119.5	C5P—C6P—H6P	119.4
C6'—C5'—C10'	120.5 (5)	C8P—C7P—C12P	116.3 (4)
C6'—C5'—H5'	119.8	C8P—C7P—P2	126.5 (3)
C10'—C5'—H5'	119.8	C12P—C7P—P2	117.1 (4)
C5'—C6'—C7'	120.6 (4)	C9P—C8P—C7P	121.5 (4)
C5'—C6'—H6'	119.7	C9P—C8P—H8P	119.3
C7'—C6'—H6'	119.7	C7P—C8P—H8P	119.3
C8'—C7'—C6'	120.9 (5)	C10P—C9P—C8P	120.5 (5)
C8'—C7'—H7'	119.5	C10P—C9P—H9P	119.7
C6'—C7'—H7'	119.5	C8P—C9P—H9P	119.7
C7'—C8'—C9'	120.7 (4)	C9P—C10P—C11P	120.1 (5)
C7'—C8'—H8'	119.7	C9P—C10P—H10P	120.0
C9'—C8'—H8'	119.7	C11P—C10P—H10P	120.0
C8'—C9'—C10'	117.9 (4)	C10P—C11P—C12P	120.0 (5)
C8'—C9'—C1'	122.3 (4)	C10P—C11P—H11P	120.0
C10'—C9'—C1'	119.8 (4)	C12P—C11P—H11P	120.0
C4'—C10'—C5'	121.5 (4)	C11P—C12P—C7P	121.5 (5)
C4'—C10'—C9'	118.9 (4)	C11P—C12P—H12P	119.2
C5'—C10'—C9'	119.4 (4)	C7P—C12P—H12P	119.2
N1—C11—C14	111.1 (4)

N1—P1—O1—C2	−67.5 (4)	C7'—C8'—C9'—C10'	0.3 (6)
O1'—P1—O1—C2	32.4 (4)	C7'—C8'—C9'—C1'	176.5 (4)
N1—P1—O1'—C2'	168.2 (3)	C2'—C1'—C9'—C8'	−171.0 (4)
O1—P1—O1'—C2'	59.0 (3)	C1—C1'—C9'—C8'	5.6 (6)
O1'—P1—N1—C12	−36.8 (5)	C2'—C1'—C9'—C10'	5.2 (5)
O1—P1—N1—C12	64.1 (5)	C1—C1'—C9'—C10'	−178.3 (3)
O1'—P1—N1—C11	147.6 (3)	C3'—C4'—C10'—C5'	173.7 (4)
O1—P1—N1—C11	−111.5 (3)	C3'—C4'—C10'—C9'	−2.0 (6)
C9—C1—C2—O1	176.4 (3)	C6'—C5'—C10'—C4'	−174.3 (4)
C1'—C1—C2—O1	−0.1 (6)	C6'—C5'—C10'—C9'	1.4 (6)
C9—C1—C2—C3	−7.9 (6)	C8'—C9'—C10'—C4'	174.8 (4)
C1'—C1—C2—C3	175.6 (4)	C1'—C9'—C10'—C4'	−1.5 (5)
P1—O1—C2—C1	−68.4 (5)	C8'—C9'—C10'—C5'	−0.9 (5)
P1—O1—C2—C3	115.6 (4)	C1'—C9'—C10'—C5'	−177.2 (3)
C1—C2—C3—C4	4.3 (7)	C12—N1—C11—C14	65.0 (5)
O1—C2—C3—C4	−179.9 (4)	P1—N1—C11—C14	−119.0 (3)
C2—C3—C4—C10	1.0 (8)	C12—N1—C11—C13	−60.6 (6)
C10—C5—C6—C7	0.1 (8)	P1—N1—C11—C13	115.4 (4)
C5—C6—C7—C8	−1.7 (8)	N1—C11—C14—C15	58.1 (5)
C6—C7—C8—C9	1.4 (7)	C13—C11—C14—C15	−175.8 (4)
C7—C8—C9—C10	0.6 (6)	C11—C14—C15—C16	−169.3 (4)
C7—C8—C9—C1	178.5 (4)	C11—C14—C15—P2	61.4 (4)
C2—C1—C9—C8	−171.3 (4)	C1P—P2—C15—C14	−175.4 (3)
C1'—C1—C9—C8	5.1 (5)	C7P—P2—C15—C14	76.7 (3)
C2—C1—C9—C10	6.6 (5)	C1P—P2—C15—C16	58.0 (4)
C1'—C1—C9—C10	−177.0 (4)	C7P—P2—C15—C16	−49.9 (4)
C3—C4—C10—C9	−2.1 (7)	C7P—P2—C1P—C6P	138.1 (3)
C3—C4—C10—C5	176.1 (5)	C15—P2—C1P—C6P	32.2 (4)
C8—C9—C10—C4	176.2 (4)	C7P—P2—C1P—C2P	−49.7 (3)
C1—C9—C10—C4	−1.7 (6)	C15—P2—C1P—C2P	−155.5 (3)
C8—C9—C10—C5	−2.0 (6)	C6P—C1P—C2P—C3P	0.1 (6)
C1—C9—C10—C5	180.0 (4)	P2—C1P—C2P—C3P	−172.6 (4)
C6—C5—C10—C4	−176.5 (5)	C1P—C2P—C3P—C4P	0.0 (7)
C6—C5—C10—C9	1.7 (7)	C2P—C3P—C4P—C5P	−0.4 (7)
C2—C1—C1'—C2'	53.2 (5)	C3P—C4P—C5P—C6P	0.8 (7)
C9—C1—C1'—C2'	−123.2 (4)	C2P—C1P—C6P—C5P	0.2 (7)
C2—C1—C1'—C9'	−123.3 (4)	P2—C1P—C6P—C5P	172.7 (4)
C9—C1—C1'—C9'	60.4 (5)	C4P—C5P—C6P—C1P	−0.7 (8)
C9'—C1'—C2'—O1'	174.2 (3)	C1P—P2—C7P—C8P	−27.0 (4)
C1—C1'—C2'—O1'	−2.5 (5)	C15—P2—C7P—C8P	80.2 (4)
C9'—C1'—C2'—C3'	−5.7 (5)	C1P—P2—C7P—C12P	156.1 (3)
C1—C1'—C2'—C3'	177.6 (4)	C15—P2—C7P—C12P	−96.7 (3)
P1—O1'—C2'—C1'	−80.1 (4)	C12P—C7P—C8P—C9P	0.0 (6)
P1—O1'—C2'—C3'	99.8 (4)	P2—C7P—C8P—C9P	−177.0 (3)
C1'—C2'—C3'—C4'	2.4 (6)	C7P—C8P—C9P—C10P	1.2 (6)
O1'—C2'—C3'—C4'	−177.5 (3)	C8P—C9P—C10P—C11P	−0.9 (7)
C2'—C3'—C4'—C10'	1.6 (6)	C9P—C10P—C11P—C12P	−0.6 (8)
C10'—C5'—C6'—C7'	−1.2 (7)	C10P—C11P—C12P—C7P	1.8 (7)
C5'—C6'—C7'—C8'	0.5 (7)	C8P—C7P—C12P—C11P	−1.5 (6)
C6'—C7'—C8'—C9'	−0.1 (7)	P2—C7P—C12P—C11P	175.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···P2	0.98	2.78	3.243 (4)	110
C12—H12A···O1′	0.96	2.48	2.862 (6)	104
C15—H15···N1	0.98	2.60	3.008 (5)	105

Puckering parameters of the P1—O1—C2—C1—C1'—C2'—O1' seven-membered ring (Cremer & Pople, 1975) top

	N-Me UPPhos, (VI)	QuinaPhos derivative (II)
Q(2)	1.005 (4) Å	0.9835 (17) Å
Φ(2)	277.0 (2)°,	95.93 (10)°
Q(3)	0.127 (4)Å	0.1464 (16) Å
Φ(3)	320.1 (19)°	150.0 (7)°
Q	1.012 (4) Å	0.9945 (17) Å

Comparison of the measured and calculated values of characteristic parameters top

Method	C12—N1—P1—O1'	C12—N1—P1—O1	O1'—C12	O1—C12	PN	PP
Crystal	-36.8 (5)	64.1 (5)	2.862 (7)	3.358 (6)	1.641 (3)	3.942 (2)
6-31G*	-47.4	51.7	2.98	3.26	1.68	3.54
SV(P)	-42.1	56.7	2.94	3.34	1.69	4.24

Ir-catalyzed asymmetric hydrogenation of N-(1-phenylethylidene)aniline, (VIII), using UPPhos^a (V) top

Entry	Precursor complex	Solvent	Pressure (bar)	Conversion (%)	ee (%)
1	[Ir(COD)₂]BAr^F₄	CH₂Cl₂	50	46	47.4^b
2	[Ir(COD)₂]BAr^F₄	CH₂Cl₂	50	99	87.7
3	[IrCl(COD)]₂	CH₂Cl₂	5	37	32.9
4	[IrCl(COD)]₂	CH₂Cl₂	25	95	75.6
5	[IrCl(COD)]₂	CH₂Cl₂	50	>99	91.8
6	[IrCl(COD)]₂	CH₂Cl₂	100	>99	91.8

Notes: (a) Reaction conditions: catalyst precursor [IrCl(COD)]₂ 0.005 mmol or [Ir(COD)₂]BAr^F₄ 0.01 mmol, UPPhos 0.011 mmol, substrate 1.25 mmol, iodine 0.05 mmol, room temperature, solvent 5 ml. (b) Without iodine additive.

Ir-catalyzed asymmetric hydrogenation of quinaldine, (XI), using UPPhos^a (V) top

Entry	Precursor complex	Solvent	Pressure (bar)	Conversion (%)	E.e. (%)
1	[IrCl(COD)]₂	CH₂Cl₂	50	67	37.1
2	[Ir(COD)₂]BAr^F₄	CH₂Cl₂	50	11	39.8
3	[IrCl(COD)]₂	CH₂Cl₂:MeOH = 1:1	50	48	63.9
4	[IrCl(COD)]₂	MeOH	50	84	70.3
5	[Ir(COD)₂]BAr^F₄	MeOH	50	39	66.3
6	[Ir(COD)₂]BAr^F₄	MeOH	100	61	69.4
7	[IrCl(COD)]₂	MeOH	150	>99	68.4

Note: (a) Reaction conditions: catalyst precursor [IrCl(COD)]₂ 0.005 mmol or [Ir(COD)₂]BAr^F₄ 0.01 mmol, UPPhos 0.011 mmol, substrate 1.25 mmol, iodine 0.05 mmol, room temperature and solvent 5 ml.

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Origin of the chemical stability of phosphine-phospho­ramidites: structural study of an UPPhos-type crystal and application of UPPhos in the asymmetric hydrogenation of imines

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Origin of the chemical stability of phosphine-phosphoramidites: structural study of an UPPhos-type crystal and application of UPPhos in the asymmetric hydrogenation of imines