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. Author manuscript; available in PMC: 2021 Jun 1.
Published in final edited form as: Angew Chem Int Ed Engl. 2021 May 2;60(23):13057–13064. doi: 10.1002/anie.202103553

Table 1.

Selected Optimization of the C−C Activation Reaction with Substrate 7a.[a]

graphic file with name nihms-1701560-t0002.jpg
Entry Catalytic conditions 7a
Conv. [%]		 6a
Yield [%][b]
1 [Rh(CO)2Cl]2 (5 mol%), P(C6F5)3 (40 mol%), THF (0.04 M), 140°C, 5 days; 50 n.d.
2[c] [Rh(COD)Cl]2 (5 mol%), dppb (12 mol%), ZnCl2 (20 mol%), THF (0.04 M), 130°C, 12h 10 5
3[c] [Rh(COD)Cl]2 (5 mol%), dppb (12 mol%), ZnCl2 (20 mol%), 1,4-dioxane (0.04 M), 130°C, 12h 57 37
4 [Rh(COD)Cl]2 (5 mol%), dppb (12 mol%), ZnCl2 (20 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 10 7
5[d] [Rh(C2H4)2Cl]2 (5 mol%), dppb (12 mol%), ZnCl2 (20 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 30 10
6 [Rh(COD)2]BF4 (10 mol%), dppb (12 mol%), ZnCl2 (20 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 93 72
7 [Rh(NBD)2]BF4 (10 mol%), dppb (12 mol%), ZnCl2 (20 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 10 5
8 [Rh(COD)MeCN]BF4 (10 mol%), dppb (12 mol%), ZnCl2 (20 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 55 45
9 [Rh(COD)2]BF4 (10 mol%), dppb (12 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 100 73
10 [Rh(COD)dppb]BF4(10 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 100 89
11 [Rh(COD)2]BF4 (10 mol%), L1 (12 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 100 60 (er 89:11)
12 [Rh(COD)2]BF4(5 mol%), L1(6 mol%), 1,4-dioxane (0.1 M), 140°C, 24h 100 83 (er 88.5:11.5)
[a]

All reactions were run on a 0.1 mmol scale.

[b]

Yields are isolated yields; numbers in parentheses are enantiomeric ratio (er) values determined by chiral HPLC.

[c]

A second portion of the same catalysts was added after 12 h.

Conv. = conversion; n.d.= not detected; COD: 1,5-cyclooctadiene; dppb: 1,4-bis(diphenylphosphino)butane; L1: (R)-(−)-DTBM-segphos.