. Author manuscript; available in PMC: 2023 Jan 26.

Published in final edited form as: Angew Chem Int Ed Engl. 2021 Dec 22;61(5):e202110519. doi: 10.1002/anie.202110519

Table 1.

Initial studies of carbene insertion into the N-H bond of N-Me aniline catalyzed by (Me)IrCYP119.^a



entry	R¹	Catalyst	er^b	Yield^b	TON^c

1	H	Purified ArM	50:50	92%	1840
2	Me	Purified ArM	40:60	56%	1120
3	Ac	Purified ArM	ND	<5%	--
4	Ts	Purified ArM	ND	<5%	--
5	Me	Cell lysis ArM	50:50	54%	1080
6^d	Me	whole cell	39:61	59%	5867
7^e	Me	whole cell	45:55	23%	2257
8^f	Me	whole cell	ND	<5%	--
9^g	Me	whole cell	ND	<5%	--

^a)

Reaction conditions: 2.5 μmol aniline derivatives, 10 μmol Me-EDA, 0.05 mol% Ir(Me)-MPIX with the CNH-0 mutant (155F, 213G, 254L, and 317G), 0.25 mL M9-N buffer, 30 °C, overnight.

^b)

The er and yield were determined by chiral HPLC with N,N-diethylaniline as the internal standard.

^c)

The TON was calculated by the number of substrate molecules converted to the product per iridium cofactor added to the cell culture.

^d)

The reactions were run in whole cells at an OD ~ 25 coexpressing the hug operon and CYP119 and 0.01 mol % Ir(Me)-MPIX.were

^e)

The reactions run in whole cells with only CYP119 expression.

^f)

The reactions run in whole cells with coexpressing the hug operon and a blank 2BT vector.

^g)

The reactions were run in whole cells coexpressing the hug operon and CYP119 but without the addition of Ir(Me)MPIX.