The first asymmetric intermolecular addition of non-acidic C–H bonds to imines is reported. The use of the activating N-perfluorobutanesulfinyl imine substituent is essential for achieving sufficient reactivity and provides outstanding diastereoselectivity (>98:2 dr). Straightforward removal of the sulfinyl group with HCl yields the highly enantiomerically enriched amine hydrochlorides.

A high yielding and practical two-step synthesis of enantiomerically pure perfluorobutanesulfinamide from Senanayake’s 2-aminoindanol-derived sulfinyl transfer reagent was developed and carried out on multi-gram scale. Straightforward condensation of this sulfinamide with ethyl glyoxylate provided the N-perfluorobutanesulfinyl imino ester. The utility of this activated N-sulfinyl imino ester was demonstrated for reactions that either gave no product or very low yields with the corresponding less electrophilic N-tert-butanesulfinyl derivative. Specifically, the Rh(III)-catalyzed C-H bond addition of aromatic compounds to the N-perfluorobutanesulfinyl imino ester provided arylglycines with very high diastereoselectivities for a range of directing groups including pyrrolidine amide, azo, sulfoximine, 1-pyrazole and 1,2,3-triazole functionality. Thermal asymmetric aza-Diels Alder reactions also proceeded in good yields and with high selectivity, including for the substituted dienes (E)-1,3-pentadiene and (2E, 4E)-2,4-hexadiene.

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The article reports preparation of (S)‐Nonafluorobutanesulfinamide. For the preparation of the perfluorobutanesulfinamide, we focused on Senanayake's chiral sulfinyl transfer auxiliary approach. The two‐step synthesis of perfluorobutanesulfinamide from Senanayakes's 2‐aminoindanol‐derived sulfinyl transfer reagent described in this report proceeds in good overall yield and with excellent enantiomeric purity. The described method uses inexpensive nonafluoro‐1‐iodobutane as a starting input and requires only one straightforward flash column chromatography. Additionally, the chiral auxiliary 3 can be recovered in good yields.

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