Table 1.

Optimization of the asymmetric allylic alkylation of fluorooxindoles.^[a]

entry	1	ligand	conditions	3	yield (%)	dr	ee (%)
							major	minor
1	1a	L1	BSA/NaOAc (3:1), 25 °C	3aa	89	2.2:1	92	92
2	1a	L2	BSA/NaOAc (3:1), 25 °C	3aa	88	1.5:1	86	94
3	1a	L3	BSA/NaOAc (3:1), 25 °C	3aa	85	1.1:1	96	93
4	1a	L4	BSA/NaOAc (3:1), 25 °C	3aa	98	2.7:1	98	96
5	1a	L5	BSA/NaOAc (3:1), 25 °C	3aa	99	2.7:1	98	96
6	1a	L6	BSA/NaOAc (3:1), 25 °C	3aa	98	3.0:1	99	98
7	1a	L7	BSA/NaOAc (3:1), 25 °C	3aa	93	2.5:1	30	28
8	1a	L8	BSA/NaOAc (3:1), 25 °C	3aa	98	1.1:1	68	60
9	1a	L9	BSA/NaOAc (3:1), 25 °C	3aa	96	1.9:1	64	72
10	1a	L10	BSA/NaOAc (3:1), 25 °C	3aa	91	2.3:1	38	28
11	1a	L6	BSA/KOAc (3:1), 25 °C	3aa	98	3.0:1	99	99
12	1a	L6	BSA/Cs2CO3 (3:1), 25 °C	3aa	88	3.1:1	99	99
13	1b	L6	BSA/KOAc (3:1), 25 °C	3ba	97	3.3:1	99	>99
14	1c	L6	BSA/KOAc (3:1), 25 °C	3ca	96	4.1:1	99	99
15	1d	L6	BSA/KOAc (3:1), 25 °C	3da	93	4.7:1	99	>99
16[b]	1a	L6	Et3N, 25 °C	3aa	99	3.1:1	>99	99
17[b]	1a	L6	iPr2EtN, 25 °C	3aa	91	2.9:1	>99	99
18[b]	1a	L6	DABCO, 25 °C	3aa	64	2.4:1	>99	99
19[b]	1a	L6	DBU, 25 °C	3aa	95	2.5:1	>99	99
20[b]	1d	L6	Et3N, 25 °C	3da	99	4.7:1	>99	99
21[b,d]	1d	L6	Et3N, 0 °C	3da	99	7.0:1	>99	>99
22[c,e]	1d	L6	Et3N, −10 °C	3da	98	9.8:1	>99	>99
23[c,f]	1d	L6	Et3N, −30 °C	3da	96	>19.0:1	>99	>99

^aAll reactions were carried out using equimolar amounts of 1 and 2, 5 mol% of the Pd complex and 12 mol% of L1-10 in dichloromethane for 14-18 hours.

^b2 Equivalents of base.

^c3 Equivalents of base.

^d24 h.

^e36 h.

^f72 h.

The ee's were determined by chiral chromatography on Chiralpak IA, Amylose I and Cellulose 3. The diastereomeric ratio was obtained from ¹⁹F NMR analysis. Boc = tert-butoxycarbonyl, BSA = bis(trimethylsilyl)acetamide, DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene, DABCO = 1,4-diazabicyclo[2.2.2]octane.