Catalytic protocols that generate a-branched amines efficiently and enantioselectively facilitate the preparation of many important biologically active molecules. [1] Among such entities are homopropargyl amines, used in the total synthesis of a number of natural products. [2] Several investigations have adopted the chiral auxiliary strategy; the desired products are obtained in high diastereoselectivity as trimethylsilyl-substituted alkynes. [3] In contrast, the corresponding catalytic protocols are scarce. The first relevant report included three examples of reactions of allenyl stannanes with a glyoxylate-derived tosylimine, [4] affording homopropargyl sulfonamides in 34-96% yield and 55:45-93:7 enantiomeric ratio (e.r.). [5] A notable recent advance entails enantioselective additions of a readily available allenylboron to tosylimines catalyzed by a Ag-phosphine catalyst to furnish a wider range of products and higher enantioselectivity (87:13 to more than 98:2 e.r.). Nonetheless, reactions of substrates that do not bear an aryl substituent proved to be less efficient, those of enolizable alkyl-substituted tosylimines were not reported and, as with the aforementioned initial development, removal of the tosyl unit requires strong reducing conditions. [6][7][8] Herein, we present a broadly applicable and efficient catalytic method for enantioselective synthesis of homopropargyl amides (Scheme 1); acid hydrolysis generates the parent amines. Transformations are performed with 0.25-2.0 mol% of a chiral N-heterocyclic carbene (NHC) complex of copper, derived from a readily available chiral imidazolinium salt and CuCl or the more robust CuCl 2 ·2H 2 O, both of which are commercially available. Aryl-, heteroaryl-, alkenyl-, as well as alkyl-substituted N-phosphinoyl imines can serve as substrates. Additions proceed to completion in seven hours or less, delivering homopropargyl amides in 65% to more than 98% yield and 92:8 to more than 98:2 e.r. The Cu-catalyzed process is amenable to gram-scale operations, and can be performed in a common fume hood without the need for strictly anhydrous and/or oxygen-free conditions. We began by probing the capacity of chiral C 1 -symmetric imidazolinium salt [9] 3a (Scheme 2), effective for reactions of allylborons with N-phosphinoyl imines, [10] in serving as the ** Financial support was provided by the NIH (GM-57212). We are grateful to Dr. B. Li for securing X-ray structures and to Frontier Scientific, Inc. for gifts of the allenylboron reagent. We thank Boston College Research Services for providing access to computational facilities.