Table 7.

NDL-catalyzed synthesis of 2-amino-4-(hetero)aryl-3,5-dicarbonitrile-6-sulfanylpyridines 11.^a

entry	Ar	R	product	t (min)	yieldb (%)	mp (°C)
						found	reported
1	phenyl: 2a	pyridyl 9	11a	30	96	222–223	224–227 [70]
2	4-methoxyphenyl: 2e	pyridyl 9	11b	35	96	248–249	250–253 [70]
3	3,4,5-trimethoxyphenyl: 2g	pyridyl 9	11c	40	92	267–269	265–268 [70]
4	3-hydroxyphenyl: 2r	pyridyl 9	11d	35	94	223–224	222–226 [70]
5	4-nitrophenyl: 2l	pyridyl 9	11e	32	96	241–243	245–248 [70]
6	4-fluorophenyl: 2m	pyridyl: 9	11f	32	95	248–250	246–249 [70]
7	4-bromophenyl: 2o	pyridyl: 9	11g	30	94	257–258	260–263 [70]
8	3,4-difluorophenyl: 2t	pyridyl: 9	11h	37	90	252–253	251–254 [70]
9	pyridyl: 2u	pyridyl: 9	11i	45	93	230–231	233–235 [70]
10	phenyl: 2a	phenyl: 10	11j	30	98	210–212	215–216 [63]
11	4-methylphenyl: 2b	phenyl: 10	11k	30	98	206–207	208–210 [69]
12	4-methoxyphenyl: 2e	phenyl: 10	11l	35	97	234–235	236–238 [64]
13	3,4,5-trimethoxyphenyl: 2g	phenyl: 10	11m	38	94	240–241	238–239 [63]
14	4-nitrophenyl: 2l	phenyl: 10	11n	30	95	280–282	286–287 [63]
15	4-fluorophenyl: 2m	phenyl: 10	11o	30	96	127–128	224–225 [69]
16	4-chlorophenyl: 2n	phenyl: 10	11p	30	96	220–221	222–223 [69]
17	3-bromophenyl: 2s	phenyl: 10	11q	34	94	250–253	256–258 [65]
18	pyridyl: 2u	phenyl: 10	11r	42	94	300–302	305–306 [63]

^aReaction conditions: aldehyde (2, 1.0 mmol), malononitrile (8, 2.0 mmol), thiol 9 or 10 (1.0 mmol), NDL (5.0 wt %), EtOH/H₂O 1:1 (3.0 mL), USI at 45–50 °C. ^bIsolated yield.