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. Author manuscript; available in PMC: 2019 Jan 17.
Published in final edited form as: J Am Chem Soc. 2018 Jan 4;140(2):598–601. doi: 10.1021/jacs.7b12213

Table 2.

Ketone Variation for Cu-Catalyzed Enantioselective Reductive Couplings with Azadiene 1aa

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entry product, Ar, R dr of 3b yield (%)c er of 6d
1e 6b, 4-MeOC6H4, Me 3.5:1 60 96.5:3.5
2 6c, 4-F3CC6H4, Me 4.0:1 50 >99:1
3 6d, 4-N-pyrazolylC6H4, Me 4.0:1 62 >99:1
4e 6e, 3-BrC6H4, Me 3.5:1 45 >99:1
5e 6f, 3-ClC6H4, Me 4.5:1 57 >99:1
6 6g, 3-HOC6H4, Me 7.5:1 62 >99:1
7e 6h, 2-BrC6H4, Me >20:1 77 99:1
8 6i, 2-MeOC6H4, Me 13.0:1 87 97:3
9 6j, 2-napthyl, Me 3.5:1 65 99:1
10 6k, 3,4-dioxolatoC6H3, Me 5.5:1 61 98.5:1.5
11 6l, 2-furyl, Me 5.0:1 55 >99:1
12 6m, 3-thiophenyl, Me 9.0:1 83 99:1
13 6n, 3-pyrrolyl(NTs), Me 5.5:1 58 95:5
14 6o, Ph, Et 10.0:1 67 99:1
15 6p, Ph, CH2CH2Ph 8.0:1 63 98:2
16 6q, 4-ClC6H4, 4-(i-PrO2CCMe2O)C6H4 1.0:1 39, 37f 99:1, 99:1g
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a

Reaction with 0.2 mmol ketone 2.

b

Diastereomeric ratio of 3 determined by 400 MHz 1H NMR spectroscopy of the unpurified mixture prior to workup.

c

Isolated yield of purified 6 (>20:1 dr).

d

Enantiomeric ratio determined by HPLC analysis of 6.

e

Cu(OAc)2· H2O used.

f

Isolated yield of each diastereomer.

g

Enantiomeric ratio of each isomer.