The synthesis of the novel electronically modified phosphinooxazoline (PHOX) ligand, (R)-5,5-dimethyl-(p-CF_3)_3-i-PrPHOX, is described. The utility of this PHOX ligand is explored in both enantio- and diastereoselective palladium-catalyzed allylic alkylations. These investigations prove (R)-5,5-dimethyl-(p-CF_3)_3-i-PrPHOX to be an effective and cost-efficient alternative to electronically modified PHOX ligands derived from the prohibitively expensive (R)-t-leucine

Craig, Robert A., II

Stoltz, Brian M.

Caltech Authors - Main

Craig, II and Stoltz  Supporting Information 
	   S1 
Synthesis and Exploration of Electronically Modified (R)-5,5-Dimethyl-(p-CF3)3-i-
PrPHOX in Palladium-Catalyzed Enantio- and Diastereoselective Allylic 
Alkylation: A Practical Alternative to (R)-(p-CF3)3-t-BuPHOX 
 
Robert A. Craig, II and Brian M. Stoltz* 
 
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical 
Engineering, Division of Chemistry and Chemical Engineering, California Institute of 
Technology, 1200 E California Boulevard, MC 101-20, Pasadena, CA 91125, USA 
 
Table of Contents 
 
Materials and Methods        S2 
 
Experimental Procedures 
 
Ligand Synthesis        S3 
 
General Procedure for Intermolecular Asymmetric Allylic Alkylation S7 
 
General Procedure for Diastereoselective Allylic Alkylation  S9 
 
Notes and References         S10 
 
NMR & IR Spectra         S11 
 
Craig, II and Stoltz  Supporting Information 
	   S2 
Materials and Methods 
Unless stated otherwise, reactions were performed at ambient temperature (23 °C) in 
flame-dried or oven-dried glassware under an argon or nitrogen atmosphere using dry, 
deoxygenated solvents (distilled or passed over a column of activated alumina)1 stirring 
with a Teflon®-coated magnetic stirring bar.  Commercially available reagents were used 
as received unless otherwise noted.  TBAT was triturated with bench-top EtOAc (25 g 
batches, 2 x 100 mL washes) under a cone of argon, dried in vacuo (ca. 0.30 torr) for 24 
hours, and then stored in a nitrogen-filled glovebox.  Et3N was distilled from calcium 
hydride immediately prior to use. Purified H2O was obtained using a Barnstead 
NANOpure Infinity UV/UF system.  4 Å molecular sieves were oven-dried at 120 °C for 
a minimum of 24 h and cooled in a desiccator to ambient temperature immediately prior 
to use.  (S)-(CF3)3-t-BuPHOX ((S)-L1),2 (S)-t-BuPHOX ((S)-L2),3 (S)-5,5-diphenyl-i-
PrPHOX ((S)-L3),4 (R)-5,5-dimethyl-i-PrPHOX ((R)-L4),5 2-bromo-5-(trifluoromethyl)-
benzoyl chloride (11),6 (R)-3-amino-2,4-dimethylpentan-2-ol hydrogen chloride (12),4,5 
bis(4-(trifluoromethyl)phenyl)phosphine oxide (15),6 and tris(4,4’-
methoxydibenzylideneacetone)-dipalladium(0) (Pd2(pmdba)3)7 were prepared by known 
methods.  Reactions requiring external heat were modulated to the specified temperatures 
using an IKAmag temperature controller.  Thin-layer chromatography (TLC) was 
performed using E. Merck silica gel 60 F254 precoated plates (250 nm) and visualized by 
UV fluorescence quenching, potassium permanganate, or p-anisaldehyde staining.  
Silicycle SiliaFlash P60 Academic Silica gel (particle size 40-63 nm) was used for flash 
chromatography.  1H and 13C NMR spectra were recorded on a Varian Inova 500 (500 
MHz and 126 MHz, respectively) are reported in terms of chemical shift relative to 
residual CHCl3 (in CDCl3, δ 7.26 and δ 77.16, respectively) or C6D5H (in C6D6, δ 7.16 
and δ 128.06, respectively).  19F and 31P NMR spectra were recorded on a Varian Mercury 
300 spectrometer (282 MHz and 121 MHz, respectively) and are reported in terms of 
absolute chemical shift according to IUPAC standard recommendations from CFCl3 and 
H3PO4, respectively.8   Data for 1H NMR spectra are reported as follows: chemical shift 
(δ ppm) (multiplicity, coupling constant (Hz), integration).  Infrared (IR) spectra were 
recorded on a Perkin Elmer Paragon 1000 Spectrometer and are reported in frequency of 
absorption (cm-1).  Analytical chiral gas chromatography was performed with an Agilent 
6850 GC using a G-TA (30 m x 0.25 cm) column (1.0 mL/minute carrier gas flow). High 
resolution mass spectra (HRMS) were obtained from the Caltech Mass Spectral Facility 
using a JEOL JMS-600H High Resolution Mass Spectrometer in fast atom bombardment 
(FAB+) ionization mode or acquired using an Agilent 6200 Series TOF with an Agilent 
G1978A Multimode source in mixed (MultiMode ESI/APCI) ionization mode.  Optical 
rotations were measured on a Jasco P-2000 polarimeter using a 100 mm path length cell 
at 589 nm. 
 
 
 
 
 
 
 
 
Craig, II and Stoltz  Supporting Information 
	   S3 
Experimental Procedures 
 
Ligand Synthesis 
 
CF3
Br O
Cl
CF3
Br O
H
N
OH
HCl•H2N OH+
11 12 13
Et3N
p-dioxane
0 °C → 23 °C
 
Benzamide 13:4 To a stirred solution of the hydrogen chloride salt of aminoalcohol 12 
(1.00 g, 5.96 mmol, 1.00 equiv) in p-dioxane (20 mL) was added Et3N (2.50 mL, 17.9 
mmol, 3.00 equiv). The reaction mixture was then cooled to 0 °C (ice/H2O bath) followed 
by the addition of acid chloride 11 (1.971 g, 6.86 mmol, 1.15 equiv) as a solution in p-
dioxane (13 mL) slowly dropwise. After 15 minutes, the reaction was removed from the 
cooling bath and allowed to warm to ambient temperature (ca. 23 °C). After 4 h, the 
consumption of starting material was complete as determined by TLC (1:9 
MeOH:CH2Cl2 eluent). The reaction mixture was concentrated in vacuo, dissolved in 
Et2O, and filtered through a pad of silica gel, eluting the product with Et2O. The filtrate 
was then concentrated in vacuo and the crude white solid residue was purified by silica 
gel column chromatography (20% acetone in hexanes eluent) to provide amide 13 (1.79 
g, 79% yield) as an amorphous white solid: Rf = 0.20 (1:4 Acetone:Hexanes eluent); 1H 
NMR (CDCl3, 500 MHz) δ 7.78–7.71 (m, 2H), 7.52 (ddt, J = 8.3, 2.3, 0.7 Hz, 1H), 6.40 
(d, J = 10.3 Hz, 1H), 4.03 (dd, J = 10.1, 2.6 Hz, 1H), 2.27 (dtd, J = 13.7, 6.8, 2.6 Hz, 1H), 
1.37 (s, 3H), 1.34 (s, 3H), 1.08 (d, J = 6.8 Hz, 3H), 1.00 (d, J = 6.8 Hz, 3H); 13C NMR 
(CDCl3, 126 MHz) δ 167.0, 139.4, 134.3, 130.4 (q, J = 33.5 Hz), 127.7 (q, J = 3.6 Hz), 
126.6 (q, J = 3.8 Hz), 123.5 (q, J = 272.3 Hz), 123.2 (q, J = 1.5 Hz), 73.8, 60.9, 29.9, 
28.8, 27.7, 22.5, 17.2; 19F NMR (CDCl3, 282 MHz) δ –62.8 (s); IR (Neat Film, NaCl) 
3413, 3299, 2964, 1638, 1540, 1332, 1311, 1173, 1132, 1080, 1033, 828 cm–1; HRMS 
Craig, II and Stoltz  Supporting Information 
	   S4 
(MM: ESI-APCI) m/z calc’d for C15H20O279BrF3N [M+H]+: 382.0624, found 382.0633; 
[α]D25.0 –3.9° (c 0.895, CHCl3). 
 
CF3
Br
CF3
Br O
H
N
OH N
O
14
13
MsOH
CH2Cl2
0 °C → reflux
 
Oxazoline 14:4  
To a solution of amide 13 (1.41 g, 3.70 mmol, 1.00 equiv) in CH2Cl2 (93 mL) at 0 °C 
(ice/H2O bath) was added methanesulfonic acid (MsOH, 1.44 mL, 22.2 mmol, 6.00 
equiv) dropwise over 10 minutes. The flask was subsequently removed from the cooling 
bath, fitted with a reflux condenser, and introduced to a preheated 50 °C bath. After 17 h, 
the consumption of starting material was complete as determined by TLC (1:4 
Acetone:Hexanes eluent). The refluxing solution was removed from the heating bath and 
allowed to cool to ambient temperature (ca. 23 °C). The yellow reaction mixture was then 
diluted with CH2Cl2 (100 mL) and poured onto saturated aqueous NaHCO3 (100 mL). 
The organics were separated and washed with H2O (40 mL) and brine (40 mL), dried 
over MgSO4, filtered, and concentrated in vacuo. The crude gold oil was purified by 
silica gel column chromatography (5%→10% acetone in hexanes eluent) to provide 
oxazoline 14 (1.18 g, 87% yield) as a pale yellow oil: Rf = 0.42 (1:9 Et2O:Hexanes 
eluent); 1H NMR (CDCl3, 500 MHz) δ 7.92–7.88 (m, 1H), 7.77–7.72 (m, 1H), 7.52–7.46 
(m, 1H), 3.53 (d, J = 8.1 Hz, 1H), 1.94 (dhept, J = 8.0, 6.6 Hz, 1H), 1.56 (s, 3H), 1.45 (s, 
3H), 1.16 (d, J = 6.5 Hz, 3H), 1.05 (d, J = 6.6 Hz, 3H); 13C NMR (CDCl3, 126 MHz) δ 
160.4, 134.6, 131.6, 129.8 (q, J = 33.4 Hz), 128.4 (q, J = 3.8 Hz), 127.9 (q, J = 3.6 Hz), 
Craig, II and Stoltz  Supporting Information 
	   S5 
126.1 (q, J = 1.7 Hz), 123.5 (q, J = 272.8 Hz), 88.2, 81.0, 29.4, 29.2, 21.4, 21.3, 20.7; 19F 
NMR (CDCl3, 282 MHz) δ –62.8 (s); IR (Neat Film, NaCl) 2973, 1652, 1608, 1472, 
1343, 1306, 1173, 1133, 1077, 1028, 830 cm–1; HRMS (MM: ESI-APCI) m/z calc’d for 
C15H18O79BrF3N [M+H]+: 364.0518, found 364.0535; [α]D25.0 +33.1° (c 6.050, CHCl3). 
 
CF3
P N
O
CF3
Br N
O F3C
CF314
CF3
P N
O
F3C
CF3
16
CuI, DMEDA
Cs2CO3
toluene
100°C
P
H
O
F3C CF3
15
Ph2SiH2
140°C
sealed
tube
O
(R)-L5
(R)-(p-CF3)3-i-PrPHOXMe2
 
(R)-5,5-dimethyl-(p-CF3)3-i-PrPHOX ((R)-L5):2a 
To a multineck reaction vessel fitted with a reflux condenser were added CuI (377 mg, 
1.98 mmol, 1.00 equiv) and phosphine oxide 15 (870 mg, 2.57 mmol, 1.30 equiv) as 
solids. The reaction vessel was then evacuated and backfilled with argon (3 x 5 minute 
cycles). Toluene (8 mL) was then added and stirring commenced. N,N’-
Dimethylethylenediamine (DMEDA, 0.64 mL, 5.94 mmol, 3.00 equiv) was then added 
dropwise causing the yellow heterogeneous reaction mixture to become dark green and 
homogeneous. After 20 minutes, oxazoline 14 (721 mg, 1.98 mmol, 1.00 equiv) was 
added as a neat oil dropwise followed by Cs2CO3 (2.39 g, 7.33 mmol, 3.70 equiv) as a 
solid in a single portion. The reaction vessel was then introduced to a preheated 110 °C 
bath. After 20 h, the consumption of starting material was complete as determined by 
TLC (1:9 Et2O:Hexanes eluent). The refluxing solution was removed from the heating 
bath and allowed to cool to ambient temperature (ca. 23 °C). The crude reaction mixture 
Craig, II and Stoltz  Supporting Information 
	   S6 
was concentrated in vacuo and the crude brown solid was purified by silica gel column 
chromatography (25%→50% EtOAc in hexanes eluent) to provide phosphine oxide 16 
(778 mg, 63% yield) as an amorphous white solid that was carried directly into the next 
transformation. 
Solid phosphine oxide 16 (778 mg, 1.25 mmol, 1.00 equiv) was added to a 
sealable pressure vessel, which was then evacuated and backfilled with argon (3 x 5 
minute cycles). To the flask was then added Ph2SiH2 (1.63 mL, 8.76 mmol, 7.00 equiv) 
with stirring. The reaction vessel, containing a homogeneous yellow solution, was then 
sealed and introduced to a preheated 140 °C bath. After 48 h, the consumption of starting 
material was complete as determined by TLC (1:1 EtOAc:Hexanes eluent). The refluxing 
solution was removed from the heating bath and allowed to cool to ambient temperature 
(ca. 23 °C). The crude reaction mixture was directly purified by silica gel column 
chromatography (20% CH2Cl2 in hexanes eluent) to furnish (R)-5,5-dimethyl-(p-CF3)3-i-
PrPHOX ((R)-(p-CF3)3-i-PrPHOXMe2, (R)-L5, 614 mg, 81% yield) as an amorphous 
white solid: Rf = 0.27 (1:4 CH2Cl2:Hexanes eluent); 1H NMR (C6D6, 500 MHz) δ 8.57 
(dd, J = 3.3, 2.0 Hz, 1H), 7.41–7.36 (m, 4H), 7.21–7.15 (m, 4H), 7.10 (dd, J = 8.2, 2.0 
Hz, 1H), 6.78 (dd, J = 8.0, 3.0 Hz, 1H), 3.22 (d, J = 8.4 Hz, 1H), 1.55 (ddt, J = 13.0, 8.3, 
6.5 Hz, 1H), 1.21 (s, 3H), 1.08 (s, 3H), 0.99 (d, J = 6.5 Hz, 3H), 0.75 (d, J = 6.5 Hz, 3H); 
13C NMR (C6D6, 126 MHz) δ 159.1 (d, J = 4.0 Hz), 143.5 (t, J = 14.8 Hz), 142.7 (d, J = 
30.6 Hz), 134.5 (dd, J = 21.3, 15.7 Hz), 133.7 (d, J = 19.5 Hz), 131.1 (q, J = 33.1 Hz), 
131.0 (dq, J = 32.3, 4.4 Hz), 127.1 (q, J = 3.6 Hz), 126.4–126.1 (m), 125.5 (dp, J = 7.5, 
3.8 Hz), 124.8 (dq, J = 272.0, 3.3 Hz), 124.4 (q, J = 272.6 Hz), 87.2, 81.7 (d, J = 1.5 Hz), 
29.1, 28.8, 21.1, 20.8, 20.8 (d, J = 1.8 Hz); 19F NMR (C6D6, 282 MHz) δ –62.6 (s), –62.9 
Craig, II and Stoltz  Supporting Information 
	   S7 
(s); 31P NMR (C6D6, 121 MHz) δ –7.1 (s); IR (Neat Film, NaCl) 2974, 1652, 1606, 1397, 
1323, 1165, 1128, 1060, 1017, 832, 756 cm–1; HRMS (FAB+) m/z calc’d for 
C29H26OF9NP [M+H]+: 606.1608, found 606.1585; [α]D25.0 +9.5° (c 3.200, CHCl3). 
 
General Procedure for Intermolecular Asymmetric Allylic Alkylation 
Ph2P N
O
t-Bu
Ph2P N
O
i-Pr
Me
Me
(S)-L2
(R)-L4 (R)-L5(S)-L3
Ph2P N
O
i-Pr
Ph
Ph
(p-CF3-C4H6)2P N
O
i-Pr
Me
Me
CF3
OO
OTES
OO
O
Cl
17 (R)-19
TBAT, Pd2(pmdba)3 
LIGAND
toluene, 35 °C
Cl
O
S
O CH3
O 18
Entry Ligand Product
1 tert-Leucine –92
2 tert-Leucine –91
3 Valine –90
4 Valine 89
(S)-L2
(S)-L1
(S)-L3
(R)-L4
Amino Acid Cost per gram ($) a
S - Enantiomer - R
33
0.60                       6
0.60                       6
351
 ee (%) b
a Cost per gram of amino acid from Sigma-Aldrich, accessed 4/30/2015. 
b Enantiomeric excess (ee) measured by analytical chiral GC.
5 Valine 91(R)-L5 0.60                       6
33 351
Amino Acid
Ligand Precursor
(S)-L1
(p-CF3-C4H6)2P N
O
t-Bu
CF3
 
Chloroallylketone 19: The procedure for the asymmetric allylic alkylation of enol ether 
17 with mesylate 18 was adapted from our previous report.9 A 20 mL scintillation vial 
was soaked in a 20:1 i-PrOH:toluene bath saturated with KOH for 12 h, rinsed with 
deionized H2O, acetone, and allowed to dry in a 120 °C oven for an additional 12 h. To 
this oven-dried 20 mL scintillation vial in a nitrogen-filled glovebox were charged 
Craig, II and Stoltz  Supporting Information 
	   S8 
Bu4NPh3SiF2 (TBAT, 216 mg, 0.40 mmol, 1.00 equiv), Pd2(pmdba)3 (7 mg, 0.006 mmol, 
0.015 equiv),  ligand (0.014 mmol, 0.035 equiv), and toluene (8.0 mL). The reaction 
vessel immediately placed into preheated 35 °C heating block with stirring. After 20 
minutes, a yellow-brown solution was observed. Chloroallylmesylate 18 (82 mg, 0.48 
mmol, 1.20 equiv) was then added quickly dropwise affording a blue-green solution. 
After 3 minutes, silyl enol ether 17 (120 mg, 0.40 mmol, 1.00 equiv) was added quickly 
dropwise. The resultant blue-green reaction mixture was allowed to stir for 20 h, at which 
time the consumption of starting material was complete as determined by TLC (1:19 
Et2O:Hexanes eluent). The resultant yellow-brown reaction was then allowed to cool to 
ambient temperature (ca. 23 °C), removed from the glovebox, filtered through a pad of 
SiO2 using hexanes as the eluent to remove toluene, at which time separate fractions were 
collected, eluting with Et2O, to isolate the semi-volatile reaction products. The filtrate 
was concentrated in vacuo to a bright yellow oil which was subsequently purified by 
silica gel column chromatography (1%→3%→5% Et2O in hexanes eluent) to afford 
semi-volatile chloroallylketone 19 as a clear, colorless oil. Rf = 0.41 (1:19 Et2O:Pentane 
eluent); characterization data match those reported in the literature.9 The ee of each 
product was determined by analytical chiral GC (G-TA column, 120 °C isotherm, major 
retention time: 53.209 min, minor retention time: 52.075 min). 
 
 
 
 
 
Craig, II and Stoltz  Supporting Information 
	   S9 
General Procedure for Diastereoselective Allylic Alkylation 
O
CO2CH2CH2TMS
Ph O Ph O Ph
Entry Ligand
2
4
(S)-L2
(R)-L5
1:2
18:1
79
85
% yield a
a Isolated yield of 22 and 23. b Determined by 
1H NMR analysis of the crude reaction mixture 
and analytical GC analysis
dr (22 :23) b
OCO2Me
TBAT (1.20 equiv)
Pd2(dba)3 (5 mol %)
LIGAND (12.5 mol %)
THF, 25 °C
21
(1.20 equiv)
22 2320
+
>99% ee
3 (R)-L2 12:173
1 L6 2:179
Ph2P N
O
L6
 
Cyclohexanone 22 and Cyclohexanone 23: The procedure for the asymmetric 
diastereoselective allylic alkylation of β-ketoester 20 with formate 21 was performed 
exactly as described in our previous report.10 The characterization data match those 
reported in the literature.10  
 
 
 
 
 
 
 
 
 
 
 
 
Craig, II and Stoltz  Supporting Information 
	   S10 
	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  	  
Notes and References 
 
1. A. B. Pangborn, M. A. Giardello, R. H. Grubbs, R. K. Rosen, F. J. Timmers, 
Organometallics 1996, 15, 1518-1520. 
2. (a) McDougal, N. T.; Streuff, J.; Mukherjee, H.; Virgil, S. C.; Stoltz, B. M. 
Tetrahedron Lett. 2010, 51, 5550–5554. (b) White, D. E.; Stewart, I. C.; Grubbs, 
R. H.; Stoltz, B. M. J. Am. Chem. Soc. 2008, 130, 810–811. (c) Tani, K.; 
Behenna, D. C.; McFadden, R. M.; Stoltz, B. M. Org. Lett. 2007, 9, 2529–2531. 
3. (a) Krout, M. R.; Mohr, J. T.; Stoltz, B. M. Org. Synth. 2009, 86, 181–193. (b) 
Behenna, D. C.; Stoltz, B. M. J. Am. Chem. Soc. 2004, 126, 15044–15045. (c) 
Peer, M.; de Jong, J. C.; Kiefer, M.; Langer, T.; Rieck, H.; Schell, H.; Sennhenn, 
P.; Sprinz, J.; Steinhagen, H.; Wiese, B.; Helmchen, G. Tetrahedron 1996, 52, 
7547–7583. 
4. Bélanger, E.; Pouliot, M.-F.; Courtemanche, M.-A.; Paquin, J.-F. J. Org. Chem. 
2012, 77, 317–331. 
5. Bélanger, E.; Pouliot, M.-F.; Paquin, J.-F. Org. Lett. 2009, 11, 2201–2204. 
6. White, D. E.; Stewart, I. C.; Grubbs, R. H.; Stoltz, B. M. J. Am. Chem. Soc. 2008, 
130, 810–811. 
7. (a) Fairlamb, I. J. S.; Kapdi, A. R.; Lee, A. F.  Org. Lett.  2004, 6, 4435–4438. (b) 
Ukai, T.; Kawazura, H.; Ishii, Y.; Bonnet, J. J.; Ibers, J. A. J. Organomet. Chem. 
1974, 65, 253–266.  
8. (a) Harris, R. K.; Becker, E. D.; Cabral de Menezes, S. M.; Granger, P.; Hoffman, 
R. E.; Zilm, K. W. Pure Appl. Chem. 2008, 80, 59–84. (b) Harris, R. K.; Becker, 
E. D.; Cabral de Menezes, S. M.; Goodfellow, R.; Granger, P. Pure Appl. Chem. 
2001, 73, 1795–1818. 
9. Craig, R. A., II; Roizen, J. L.; Smith, R. C.; Jones, A. C.; Stoltz, B. M. Org. Lett. 
2012, 14, 5716–5719. 
10. Liu, W.-B.; Reeves, C. M.; Virgil, S. C.; Stoltz, B. M. J. Am. Chem. Soc. 2013, 
135, 10626–10629.	  
Craig, II and Stoltz  Supporting Information  
 S11 








	





NMR & IR Spectra 
 
 
  
1 H
 N
M
R
 (5
00
 M
H
z,
 C
D
C
l 3
) o
f c
om
po
un
d 
13
. 
 
 
CF
3
Br
O
H N
O
H
13
Craig, II and Stoltz  Supporting Information  
 S12 


  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Infrared spectrum (Thin Film, NaCl) of compound 13. 
13C NMR (126 MHz, CDCl3) of compound 13. 
Craig, II and Stoltz  Supporting Information  
 S13 





































	
 
  
 
 
  
19
F 
N
M
R
 (2
82
 M
H
z,
 C
D
C
l 3
) o
f c
om
po
un
d 
13
. 
 
 
CF
3
Br
O
H N
O
H
13
Craig, II and Stoltz  Supporting Information  
 S14 








	





  
   
1 H
 N
M
R
 (5
00
 M
H
z,
 C
D
C
l 3
) o
f c
om
po
un
d 
14
. 
 
 
CF
3
Br
N
O
14
Craig, II and Stoltz  Supporting Information  
 S15 


  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Infrared spectrum (Thin Film, NaCl) of compound 14. 
13C NMR (126 MHz, CDCl3) of compound 14. 
Craig, II and Stoltz  Supporting Information  
 S16 





































	
 
 
  
 
  
19
F 
N
M
R
 (2
82
 M
H
z,
 C
D
C
l 3
) o
f c
om
po
un
d 
14
. 
 
 
CF
3
Br
N
O
14
Craig, II and Stoltz  Supporting Information  
 S17 








	







  
   
 1
H
 N
M
R
 (5
00
 M
H
z,
 C
6D
6)
 o
f c
om
po
un
d 
(R
)-
L5
. 
 
 
CF
3
P
N
O
F 3
C
CF
3
(R
)-L
5
(R
)-(
p-
CF
3)
3-i
-P
rP
HO
XM
e 2
Craig, II and Stoltz  Supporting Information  
 S18 


  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Infrared spectrum (Thin Film, NaCl) of compound (R)-L5. 
13C NMR (126 MHz, C6D6) of compound (R)-L5. 
Craig, II and Stoltz  Supporting Information  
 S19 





































	
 
 
 
 
  
19
F 
N
M
R
 (2
82
 M
H
z,
 C
6D
6)
 o
f c
om
po
un
d 
(R
)-
L5
. 
 
 
CF
3
P
N
O
F 3
C
CF
3
(R
)-L
5
(R
)-(
p-
CF
3)
3-i
-P
rP
HO
XM
e 2
Craig, II and Stoltz  Supporting Information  
 S20 
































	
  
  
 
 3
1 P
 N
M
R
 (1
21
 M
H
z,
 C
6D
6)
 o
f c
om
po
un
d 
(R
)-
L5
. 
 
 
CF
3
P
N
O
F 3
C
CF
3
(R
)-L
5
(R
)-(
p-
CF
3)
3-i
-P
rP
HO
XM
e 2


English

Synthesis and exploration of electronically modified

(R)-5,5-dimethyl-(p-CF_3)_3-i-PrPHOX in palladium-catalyzed

enantio- and diastereoselective allylic alkylation: a practical alternative to (R)-(p-CF_3)_3-t-BuPHOX

http://authors.library.caltech.edu/58771/3/nihms705028.pdf

Synthesis and exploration of electronically modified (R)-5,5-dimethyl-(p-CF_3)_3-i-PrPHOX in palladium-catalyzed enantio- and diastereoselective allylic alkylation: a practical alternative to (R)-(p-CF_3)_3-t-BuPHOX

Abstract

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