Table 1.

Optimization of the allylic C-H functionalization reaction^[a]

entry	Catalyst	Additive	Yield[b]	d.r. [c]	ee[d]
1	Rh2(S-NTTL)4	----	72%	3:1	92/84
2	Rh2(S-NTTL)4	HFIP	81%	3:1	96/85
3	Rh2(S-NTTL)4	NFTB	76%	3:1	95/87
4	Rh2(S-PTAD)4	HFIP	53%	2:1	80/77
5	Rh2(R-PTTL)4[e]	HFIP	64%	1.5:1	−82/−84
6	Rh2(S-NTTLCl)4	HFIP	77%	3:1	93/86
7	Rh2(S-TPPTTL)4	HFIP	<5%	nd	nd
8	Rh2(S-TCPTAD)4	HFIP	14%	1:1	89/92

^[a]Reaction conditions: 9 (2.0 mmol), 10 (0.5 mmol), [Rh] catalyst (1 mol %), 16–18 h reaction time, additive (2 equiv), LiAlH₄ (2 equiv).

^[b]combined isolated yield of 12a and 12a’

^[c]determined by crude NMR

^[d]major/minor diastereomer ee dtermined by chiral HPLC analysis of the isolated products

^[e]observed opposite enantiomers. HFIP= Hexafluoroisopropanol, NFTB = Nonafluoro-tert-butyl alcohol