*3.2. Methods*

3.2.1. Preparation of 1-Alkenyl Phosphine Sulfides **3a**–**c**, **4a** and **5**, **6** via Ethylmagnesium Bromide and Titanium(IV) Isopropoxide-Catalyzed Reaction of 1-Alkynyl Phosphine Sulfides with Et2Zn

(*Z*)-(2-Ethylhex-1-en-1-yl)diphenylphosphine sulfide (**3a**). Typical Procedure. To a solution of hex-1-yn-1-yldiphenylphosphine sulfide (596 mg, 2 mmol) and Et2Zn (1 M in hexanes, 5 mL, 5 mmol) in ether (6 mL) was added Ti(O-iPr)4 (0.5 M in hexanes, 0.6 mL, 0.3 mmol). Ethylmagnesiurn bromide (2.5 M in Et2O, 0.16 mL, 0.4 mmol) was then was added dropwise, and the reaction mixture turned black. After 18 h at room temperature, the mixture was diluted with Et2O (5 mL), and 25 wt % aq. KOH (3 mL) was added dropwise while the flask was cooled in an ice bath. The aqueous phase was extracted with Et2O (3 × 5 mL). The combined organic phase was washed with a saturated aqueous solution of NaCl (10 mL) and dried over anhydrous MgSO4. The reaction mixture was filtered and concentrated in vacuo to give the crude product as a yellow oil. Evaporation of the solvent and purification of the residue by column chromatography (hexane:ethyl acetate:methanol = 5:2:1)) gave **3a** (538 mg, 82%) as a colorless oil. *R*f 0.42. 1H NMR (δ, ppm, *J*/Hz): 0.73 (t, *J* = 7.3, 3H, C(12)H3), 1.00–1.10 (m, 2H, C(11)H2), 1.13 (t, *J* = 7.4, 2H, C(8)H3), 1.20–1.30 (m, 2H, C(10)H2), 2.29 (q, *J* = 7.5, 2H, C(7)H2), 2.37 (t, *J* = 7.4, 2H, C(9)H2), 6.03 (d, J = 23.5, 2H, C(7)H2), 7.25–8.00 (m, 10H, Ph). 13C NMR (δ, ppm, *J*/Hz): 12.17 (C(8)), 13.79 (C(12)), 22.80 (C(11)), 29.48 (C(10)), 31.21 (d, *J* = 16.4, C(7)), 33.92 (d, *J* = 9.3, C(9)), 115.99 (d, *J* = 89.4, C(5)), 128.43 (d, *J* = 12.3, 4C, C(3)), 131.01 (d, *J* = 2.5, 2C, C(4)), 131.20 (d, *J* = 10.5, 4C, C(2)), 135.21 (d, *J* = 84.2, 2C, C(1)), 168.22 (C(6)). 31P NMR (δ, ppm): 28.68.MS (EI): m/z, % = 328 (45) [M+], 299 (18), 254 (4), 218 (100), 183 (48), 139 (30), 108 (18), 41 (17). Anal. calcd for C20 H25PS, (%): C, 73.14; H, 7.67. Found, %: C, 73.20; H, 7.71. The 1H NMR and 13C NMR of the compounds **3b**,**c**, **4a**, **5**, **6** data of coupling products were shown in the Supplementary Materials.

3.2.2. Preparation of 1-Alkenyl Phosphine Oxides **12a**, **13b**, **13c**, **14c**, **16**, and **17** via Titanium(IV) Isopropoxide and Ethylmagnesium Bromide-Catalyzed Reaction of 1-Alkynyl Phosphines with Et2Zn

(*Z*)-(2-(Ethyl-2-d)oct-1-en-1-yl-1-d)diphenylphosphine oxide (**12a**). Typical Procedure. To a solution of oct-1-yn-1-yldiphenylphosphane (588 mg, 2 mmol) and Et2Zn (1 M in hexanes, 5 mL, 5 mmol) in dichloromethane (5 mL) was added Ti(OPr-i)4 (0.5 M in hexanes, 0.6 mL, 0.3 mmol). Ether solution of EtMgBr (2.5 M in Et2O, 0.16 mL, 0.4 mmol) was then added, and the mixture turned black. After 48 h at room temperature, CH2Cl2 (5 mL) was added to the reaction mixture, and D2O (3 mL) was added dropwise while the flask was cooled in an ice bath. The aqueous inorganic layer was extracted through CH2Cl2 (3 × 5 mL). The combined organic phase was washed sequentially with water and brine (10 mL) and dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure. A 30% hydrogen peroxide solution (0.35 mL, 3 mmol) was slowly added dropwise with vigorous stirring to a solution of the crude residue (2-(Ethyl-2-d)oct-1-en-1-yl-1-d)diphenylphosphine oxide, in chloroform (5 mL). The reaction mixture was stirred for 1 h and washed with water (3 × 5 mL), the organic layer was dried over MgSO4. The reaction mixture was filtered through a filter paper and concentrated in vacuo to give crude product as a yellow oil that was purified by column chromatography (silica gel, hexane:ethyl acetate:methanol = 5:2:1) to a fford **12a** (445 mg, 65%). *R*f 0.59. The spectral properties (1H NMR, 13C NMR, MS) were in good agreemen<sup>t</sup> with those that were reported in the literature [33]. The 1H NMR and 13C NMR of the compounds **13b**, **13c**, **14c**, **16**, **17** data of coupling products are shown in the Supplementary Materials.

3.2.3. Preparation of Allylic Amines **8a**, **9a**–**d** via Titanium(IV) Isopropoxide and Ethylmagnesium Bromide-Catalyzed Reaction of 2-Alkynylamines with Et2Zn

(*Z*)-3-(Ethyl-2-d)- *<sup>N</sup>*,*<sup>N</sup>*-dimethylhept-2-en-1-amine-2-d (**8a**). Typical Procedure. To 278 mg of *<sup>N</sup>*,*<sup>N</sup>*-dimethylhept-2-yn-1-amine (2 mmol) and 5 mL of Et2Zn (1 M in hexanes, 5 mmol) suspended in 6 ml hexane was added under an atmosphere of argon Ti(OPr-i)4 (0.5 M in hexanes, 0.6 mL, 0.3 mmol). Then sequentially, EtMgBr (2.5 M in Et2O, 0.16 mL, 0.4 mmol) was added, and the mixture turned

black. After 18 h at room temperature, the reaction mixture was diluted with Et2O (5 mL), and D2O (3 mL) was added dropwise while the flask was cooled in an ice bath. The aqueous layer was extracted with Et2O (3 × 5 mL). The organic layers were washed with brine (10 mL), dried over anhydrous CaCl2. The reaction mixture was filtered through a filter paper and concentrated in vacuo to give crude product as a yellow oil. The residue was distilled through a micro column at 10 mmHg to give 8a (287 mg, 84%) as a colorless oil. b.p. 87–89 ◦C (10 mmHg) (lit. 7 b.p. 91–93 ◦C (15 mmHg)). 1H NMR (400MHz, CDCl3): δ = 0.92 (t, *J* = 6.3 Hz, 3H, C(11)H3), 1.00 (t, *J* = 7.7 Hz, 3H, C(5)H3), 1.25–1.40 (m, 4H, C(9,10)H2), 2.03 (t, *J* = 7.8 Hz, 2H, C(4)H2), 2.10–2.35 (m, 2H, C(8)H2), 2.23 (s, 6H, C(6,7)H3), 2.90 (s, 2H, C(1)H2). 13C NMR (100 MHz, CDCl3): δ = 12.41 (t, C(5), <sup>1</sup>*J*CD = 19.3 Hz), 14.02 (C(11)), 22.84 (C(10)), 29.41 and 30.30 and 30.71 (C(4,8,9)), 45.26 (2C(6,7)), 56.77 (C(1)), 144.27 (C(3)).

MS (EI): m/z, % = 171 (14) [M+], 142 (10), 126 (18), 112 (21), 95 (100), 82 (32), 58 (49), 46 (48). Anal. calcd for C11H21D2N, (%): C, 77.12. Found, %: C, 77.21. The 1H NMR and 13C NMR of the compounds **9a**–**d** data of coupling products are shown in the Supplementary Materials.

### 3.2.4. The Iodination of Intermediate Organozinc Compounds

(*Z*)-2-Iodo-3-(2-iodoethyl)-*<sup>N</sup>*,*<sup>N</sup>*-dimethylnon-2-en-1-amine (**10d**). Typical Procedure. To a solution of *<sup>N</sup>*,*<sup>N</sup>*-dimethylnon-2-yn-1-amine (334 g, 2 mmol) and Et2Zn (1 M in hexanes, 5 mL, 5 mmol) in toluene (6 mL) was added Ti(OPr-i)4 (0.5 M in hexanes, 0.3 mL, 0.2 mmol) followed by ethylmagnesium bromide (2.5 M in Et2O, 0.16 mL, 0.4 mmol). After 18 h at 23 C, the reaction mixture was cooled to −78 ◦C, and a solution of I2 (1575 mg, 12.5 mmol) in THF (12.5 mL) was added via cannula. The mixture was warmed to room temperature and stirred for 10 h. The mixture was then treated by a 25% water solution of KOH and Et2O. The organic phase was washed with water and an aqueous solution of Na2S2O3, drying with MgSO4. Evaporation of the solvent and purification of the residue by column chromatography (hexane/ethyl acetate, 5:1) gave a yellow oil; yield: 503 mg, (56%); *R*f = 0.73 (hexane/ethyl acetate, 5:1). The spectral properties (1H NMR, 13C NMR, MS) of the compounds **10d**, **10e** were in good agreemen<sup>t</sup> with those that were reported in the literature [1].
