Table 1.

Addition of organolithium/Grignard reagents (RLi/RMgX) to benzonitrile (1a) under air, at room temperature and in the absence of any additional/external solvent.^[a]

Entry	R‐Li[b]	Equiv.	Ketone	Yield [%][c]
1	MeLi	1	3a	99
2	EtLi	1	3n	15
3	EtLi	2	3n	79
4	n‐BuLi	1	3o	74
5	n‐BuLi	2	3o	86
6	PhLi	1	3p	60
7	2‐thienylLi	1	3q	84
8	(CH3)3SiCH2Li	3	3a	58
9	n‐BuMgCl	3	3o	61

[a] General conditions: reactions performed under air/moisture, at room temperature and in the absence of external organic solvents, using 0.5 mmol of benzonitrile (1a). [b] Commercial solution of MeLi (1.6 M in diethyl ether), EtLi (0.5 M in benzene/cyclohexane), n‐BuLi (2.5 M in hexanes), PhLi (1.9 M in n‐Bu₂O), 2‐thienyl lithium [1 M in tetrahydrofuran (THF)/hexanes], (CH₃)₃SiCH₂Li (1 M in pentane) and n‐BuMgCl (2 M in Et₂O) were employed. [c] Yields determined by ¹H nuclear magnetic resonance (NMR) spectroscopy using trimethoxybenzene as internal standard (0.5 mmol) (see Supporting Information).