. Author manuscript; available in PMC: 2017 Oct 17.

Published in final edited form as: Angew Chem Int Ed Engl. 2016 Sep 20;55(43):13562–13566. doi: 10.1002/anie.201607278

Table 1.

Myoglobin-catalyzed tandem sulfur ylide formation and [2,3]-sigmatropic rearrangement of phenyl allyl sulfide with EDA.^[a]


Entry	Catalyst	Deviation from s.r.c.	% conv.^[b]	TON^[c]
1	WT Mb	-	44%	445
2	WT Mb	aerobic	0%	0
3	WT Mb	no Na₂S₂O₄	19%	195
4	WT Mb	1 equiv. 2a	19%	185
5	WT Mb	0.5 equiv. 2a	11%	115
6	Mb(L29S,H64V,V68F)	-	>99%	>995
7	Mb(L29S,H64V,V68F)	0.025 mol%	87%	3,500
8	Mb(L29S,H64V,V68F)	0.01 mol%	63%	6,270
9	Mb(L29S,H64V,V68F)	30 min	>99%	>995

^[a]

Standard reaction conditions (s.r.c.) = 10 mM 1, 20 mM 2a, 10 μM Mb catalyst (0.1 mol%), 10 mM Na₂S₂O₄ in oxygen-free potassium phosphate buffer (50 mM, pH 8) at room temperature.

^[b]

As determined by gas chromatography.

^[c]

= nmol product / nmol catalyst. Errors are within ± 10%.