Table 1. Substrate scope of the zinc sulfinate salt toolkit.

Isolated yields are displayed, % conversions by GC-MS are indicated between parentheses, and regioisomeric ratios are shown between square brackets. Compounds 1A, 2A, 3A, 4A and 5A have been previously synthesized with Langlois’ reagent (ref. 7); 1B, 2B, 3B, 4B, 5B and 8B have been previously prepared using DFMS (ref. 9) and are included herein for completeness; all other compounds in this table are new.

Zn salt; R =	CF3 (A)	CF2H (B)	CF2CF3 (C)	CF2F (D)	CH(CH3)2 (E)	(CH2CH2O)3CH3 (F)
heterocycle
1	89 (100)b	73 (57)bk	51g	80g	41h	40i
	1A	1B	1C	1D	1E	1F
2	79 (100)b	72 (41)bk	44g	75g	37h	49i
	2A	2B	2C	2D	2E	2F
3	35 (77)b [4:1 C2:C3]	66 (100)b	18 (85)g [4:1 C2:C3]	73fj [17:1 C2:C2&C6]	47d	41i
	3A	3B	3C	3D	3E	3F
4	66 (65)bk [2.3:1 C6:C2]	60 (96)b	33g [1.4:1 C6:C4]	N.R.	41i	N.R.
	4A	4B	4C	4D	4E	4F
5	75 (100)b [5 products]	50 (67)b	31 (77)c	56g	43h	32h
	5A	5B	5C	5D	5E	5F
6	42 (44)e [2.7:1 C4:C5]	21 (44)e [1.6:1 C4:C5]	21h	N.R.	46h [2.1:1 C4:C5]	16i [3.4:1 C4:C5]
	6A	6B	6C	6D	6E	6F
7	45 (90)e	57 (71)e [6:1 C4:C5]	N.R.	N.R.	49h [10:1 C4:C5]	32 (38)i
	7A	7B	7C	7D	7E	7F
8	76 (91)b [7.4:1 C2:C5]	65 (100)b	58h [1.4:1 C2:C5]	40d	17h	10 (43)i
	8A	8B	8C	8D	8E	8F

^aStandard conditions involve heterocycle (1.0 equiv), zinc salt (2.0–3.0 equiv), TBHP (3.0–5.0 equiv) and solvent:H₂O (2.5:1) at a specified temperature for a period of 3–12 h. Solvent/temperature:

^bCH₂Cl₂, RT;

^cClCH₂CH₂Cl, RT;

^dClCH₂CH₂Cl, 50 °C;

^eperfluorohexane, RT;

^fperfluorotoluene, RT;

^gperfluorotoluene, 50 °C;

^hDMSO, 50 °C;

ⁱanisole, 50 °C (note: the reaction time for anisole is 0.5–96 h, see Supplementary Information).

^jTFA was used as an additive.

^kWhen the GC % conversion is lower than the isolated yield, it signifies that only one addition of Zn salt was made for the “GC yield reaction”, but that a second addition of Zn salt and TBHP was performed after 12 h for the “isolated yield reaction”.

TBHP = tert-butyl hydroperoxide; TFA = trifluoroacetic acid; RT = room temperature; N.R. = no reaction.