Table 1 Selected Optimizationsa
From: Controlled chain-growth polymerization via propargyl/allenyl palladium intermediates
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|---|---|---|---|---|---|---|---|---|---|
Entry | x | L | Base | T (°C) | Note | Conv. (%) | Yield (%) | Mn,GPC (kg/mol) | Đ |
1 | 1 | DPEPhos | NaOtBu | 40 | >99 | 75 | 11.9 | 1.22 | |
2 | 1 | DPEPhos | 40 | 91 | <5 | ||||
3 | 1 | DPEPhos | 40 | w/o 1a | 91 | <5 | |||
4 | 1 | DPEPhos | NaOtBu | 40 | w/o 1a | >99 | 79 | 82.1 | 1.73 |
5 | DPEPhos | NaOtBu | 40 | 18 | |||||
6 | 1 | DPEPhos | LiOtBu | 40 | >99 | 77 | 8.8 | 1.13 | |
7 | 1 | DPEPhos | KOtBu | 40 | >99 | 69 | 9.3 | 1.16 | |
8 | 1 | DPEPhos | DBU | 40 | >99 | 38 | 2.8 | 1.29 | |
9 | 1 | DPEPhos | NaOtBu | 40 | in DMSO | >99 | 19 | 8.1 | 1.21 |
10 | 1 | DPEPhos | NaOtBu | 40 | in MeCN | >99 | 82 | 9.4 | 1.18 |
11 | 1 | DPEPhos | NaOtBu | 40 | in PhMe | >99 | 79 | 16.5 | 1.40 |
12 | 1 | rac-BINAP | NaOtBu | 40 | >99 | 71 | 11.4 | 1.20 | |
13 | 1 | dppe | NaOtBu | 40 | 52 | ||||
14 | 1 | NaOtBu | 40 | 57 | |||||
15 | 1 | PPh3 | NaOtBu | 40 | >99 | 62 | 10.3 | 1.18 | |
16 | 1 | PCy3 | NaOtBu | 40 | 54 | ||||
17 | 1 | DPEPhos | NaOtBu | r.t. | >99 | 78 | 9.8 | 1.20 | |
18 | 0.25 | DPEPhos | NaOtBu | r.t. | >99 | 84 | 9.2 | 1.08 | |
19 | 0.25 | DPEPhos | NaOtBu | r.t. | reaction time = 5 min | >99 | 72 | 8.5 | 1.08 |
