Summary of steps in the synthesis of aromatic diazirines. MsCl: mesyl chloride; Py: pyridine; pTsCl: p-tosyl chloride; DMAP: N,N-dimethyl-4-aminopyridine.

Step	Synthetic conditions	Ref.
A1	n-BuLi, ether, CF3COOEt, −78 °C, 2 h	49,53
	n-BuLi, THF, CF3COOMe, −78 °C, 2 h	54
	Mg, CF3COR, R = piperidinyl	55
	Mg/CF3COOH or n-BuLi/CF3COR, R = OMe, piperidinyl	20
A2	(1) TMS-CF3, catalytic TBAF, THF; then aqueous HCl	56
	(2) Dess-Martin periodinane, TFA, CH2Cl2
	(1) TMS-CF3, K2CO3, DMA, rt, 2 h	57
	(2) 1 M HCl, rt, 1 h
	(3) Dess-Martin, CH2Cl2, rt, 8 h
B1	NH2OH, NaOH, EtOH, reflux, 21 h	49
	NH2OH·HCl, pyridine, EtOH, 60 °C, 4 h	53–58
	NH2OH·HCl, NaOH, EtOH, reflux, 16 h or pyridine, 70 °C, 3 h	59
B2	1 M LiN(TMS)2 in THF, toluene, 0 °C	51
C	MsCl, TEA	49
	TsCl, pyridine, reflux	2,53,54,56,59
	TsCl, TEA, N,N-dimethylaminopyridine, CH2Cl2, 0 °C, 45 min	55
	TsCl, DMAP, TEA, CH2Cl2, rt, 45 min	57
D1	NH3 (l), CH2Cl2, −78 °C	49,54,55
	NH3 (l), ether, −78 °C→rt or rt	53,56,57,59
	NH3 (l), 80 °C, 20 h	58
D2	NH3 (l), LiNH2, rt, 11 h	50,57,59
M	MeOH, 18 h	51
N	(1) in THF, 0 °C	51
	(2) piperidine
E	Ag2O, ether, 23 °C, 3.5 h	49,54
	tert-BuOCl, TEA	2,55
	I2, TEA, CH2Cl2 or MeOH, 0 °C	56,58,59
	MnO2, ether or CH2Cl2, rt	53,57
	(COCl)2, DMSO, DCM, −78 °C	60