Formal Carbon Insertion of N-Tosylhydrazone into B-B and B-Si Bonds: gem-diborylation and gem-silylborylation of sp 3 Carbon

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1 Formal Carbon Insertion of N-Tosylhydrazone into B-B and B-Si Bonds: gem-diborylation and gem-silylborylation of sp 3 Carbon Huan Li, Xianghang Shangguan, Zhikun Zhang, Shan Huang, Yan Zhang and Jianbo Wang* Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 1871, China wangjb@pku.edu.cn 1. General.... S2 2. General procedures for reactions of tosylhydrazones with B 2 pin 2 and silylborane... S2 3. Derivatization of 1,1-diboronates... S4 4. General procedure for stepwise coupling reactions of 1,1-diboronate 2a with aryl bromides and aryl iodides... S5 5. General procedure for allylboration of 2r with aldehyde... S5 6. Spectra data S6 7. References.. S H and 13 C spectra... S16 S1

2 1. General All reactions were performed under a nitrogen atmosphere in an oven-dried reaction flask. All solvents were distilled prior to use. Toluene and 1,4-dioxane were dried over Na before use. For chromatography, 2-3 mesh silica gel (Qingdao, China) was employed. 1 H NMR and 13 CNMR spectra were recorded on Brucker ARX 4 MHz spectrometer in CDCl 3 solution and the chemical shifts were reported in parts per million (δ) relative to internal standard TMS ( ppm). Unless otherwise noted, materials obtained from commercial suppliers were used without further purification. 2. General procedures for reactions of tosylhydrazones with B 2 pin 2 and silylborane 2.1 General procedure for preparation of tosylhydrazones a) For alkyl aldehydes: A round-bottomed flask was charged with aldehydes (1 mmol) and tosylhydrazine (1 mmol). Then methanol (5 ml) was added. The mixture was stirred at room temperature. N-Tosylhydrazone precipitated after 15 minutes or longer and the reaction was monitored by TLC analysis (the spot of carbonyl compound). The precipitate was then collected, washed with petroleum ether (5 ml 3), and dried in vacuum. b) For other types of aldehydes and ketones: When the carbonyl compound is solid, both carbonyl compound (1 mmol) and tosylhydrazine (1 mmol) were dissolved in methanol (5 ml) separately. Then the solution of carbonyl compound was added to the solution of tosylhydrazine. When the carbonyl compound was liquid, tosylhydrazine (1 mmol) was dissolved in methanol (1 ml), and carbonyl compound was added later. The mixed solution was heated at 7 o C. TLC analysis was performed until the spot of carbonyl compound disappeared. Then the solution was cooled down, and N-tosylhydrazone precipitated. The precipitate was collected, washed with petroleum ether (5 ml 3), and dried in vacuum. 2.2 General procedure for reactions of tosylhydrazones with B 2 pin 2 A modified Schlenk tube was charged with N-tosylhydrazone (1 mmol), 6% NaH (1.2 mmol, 48 mg), and BTMAC (.1 mmol, 19 mg) if needed. After degassed and filled with N 2, the tube was charged with toluene (8 ml) or dioxane (8 ml). The mixture was stirred at room temperature for 1 h. Then a solution of B 2 pin 2 (1.2 mmol, 35 mg) in toluene (2 ml) or dioxane (2 ml) was added via syringe. Then the tube was sealed and heated at 11 o C for 12 h. After cooled to room temperature, 1 ml of Et 2 and 1 ml of H 2 were added. The mixture was stirred vigorously for 1 minutes. After separation of organic layer, the aqueous layer was extracted with Et 2 (5 ml 2). The combined organic solution was washed with saturated S2

3 brine (1 ml) and dried over anhydrous Na 2 S 4. After the solvent was evaporated, the crude product was purified by silica gel chromatography. 2.3 ptimization for diborylation of hydrazones derived from ketones a Entry Solvent Additives (mol%) T ( o C) Time (h) Yield 1 Toluene Trace 2 DMF % 3 dioxane < 5% 4 dioxane % 5 dioxane BTMAC (1) % 6 dioxane BTMAC (1) % a Reaction conditions: tosylhydrazone (1 mmol), NaH (1.2 mmol), additives (.1 mmol), B 2 pin 2 (1.2 mmol), solvent (8 ml+2 ml). Product was isolated by silica gel column chromatography. 2.4 Large scale preparation of diboronate 2a Procedure was followed as described above. N-Tosylhydrazone (1.87 g, 36 mmol), NaH (1.68 g, 42 mmol), B 2 pin 2 (7.62 g, 3 mmol), 12 ml (1 ml+2 ml) of toluene were used. Caution: due to the release of large amount of N 2, a N 2 balloon was linked to the flask to balance the pressure. Hexane (5 ml) was added to the crude product. Then the mixture was added at 9 o C until the solid dissolved. After cooled down and placed at room temperature overnight, 2a precipitated from the solution. Then the precipitate was collected and washed with hexane (5 ml 2). Then the residue was combined, concentrated and recrystallized. After both of the precipitates were dried in vacuum, a white powder was obtained (9.49 g, 85%). 2.5 General procedure for reactions of tosylhydrazones with silylborane S3

4 A modified Schlenk tube was charged with N-tosylhydrazone (.5 mmol), 6% NaH (48 mg,.6 mmol). After degassed and filled with N 2, the tube was charged with toluene (5 ml). The mixture was stirred at room temperature for 1 h. Then silylborane reagent 1 (157 mg,.6 mmol) was added through micro syringe. Then the tube was sealed and heated at 11 o C for 12 h. After cooled to room temperature, the mixture was filtrated through a pad of silica gel and washed with Et 2. Then the solvent was evaporated in vacuum, and the product was purified by silica gel chromatography. 3. Derivatization of 1,1-diboronates 3.1 Reductive amination of 2s 2s was prepared according to the standard procedure, and isolated as a mixture containing the remaining B 2 pin 2 due to almost the same polarity. After charged with 1% Pd/C (.1 mmol), the modified Schlenk tube was degassed and filled with H 2. The solution of 2s in MeH (5 ml) was added through syringe. The mixture was stirred at 25 o C for 24 h. The mixture was filtrated through a pad of silica gel and washed with Et 2. Then the solvent was evaporated off in vacuum. After purified by silica gel chromatography (elute solution: PE/EA, 5:1 v/v), 2t was obtained as a white solid (228 mg, 59% yield for 2 steps). 3.2 Reduction of 2u and oxidation of 2v 2u was prepared according to the standard procedure, and isolated as a mixture containing the remaining B 2 pin 2 due to their similar polarity. A modified Schlenk tube (25 ml) was degassed and filled with N 2. The solution of 2u in THF (5 ml) was added through syringe. S4

5 Then the tube was cooled in an ice-water bath. DIBAL-H (1 M in toluene, 3 ml) was added though syringe. The mixture was slowly warmed to room temperature and stirred at room temperature for 24 h. Then 1 M HCl (1 ml) was added. After stirred for 15 minutes, the organic layer was separated and the aqueous layer was extracted with Et 2 (1 ml 2). The combined organic layer was washed with saturated brine (1 ml) and dried over anhydrous Na 2 S 4. Then solvent was evaporated in vacuum. After purified by silica gel chromatography (elute solution: PE/EA, 5:1 v/v), 2v was obtained as a white solid (321 mg, 8% yield for 2 steps). A round-bottomed flask was charged with 2v (.5 mmol), and CH 2 Cl 2 (2 ml) was added. Then the tube was placed in an ice-water bath. DMP (.65 mmol) was added. The mixture was stirred at 1 minutes and slowly warmed to room temperature. The reaction was monitored by TLC analysis. The mixture was filtrated through a pad of silica gel and washed with Et 2. The organic layer was combined. Then solvent was evaporated off in vacuum. After purified by silica gel chromatography (elute solution: PE/EA, 1:1 v/v), 2w was obtained as a white solid (162 mg, 81% yield). 4. General procedure for stepwise coupling reactions of 1,1-diboronate 2a with aryl bromides and aryl iodides Ph Bpin Bpin Ar 1 Br (1.5 equiv) Pd(PtBu 3 ) 2 (5 mol%) KH (1 M; 2 equiv) dioxane-h 2 25 o C, 6 h Ph 4a-e Bpin Ar 1 Ar 2 I (1.2 equiv) Pd 2 dba 3 (5 mol%) PPh 3 (1 equiv) Ag 2 (1.5 equiv) dioxane, 9 o C, 24 h Ph 5a-e Ar 1 Ar 2 Step 1: a microwave tube (1 ml) was charged with 2a (.2 mmol), Pd(PtBu 3 ) 2 (.1 mmol), aryl bromide (.3 mmol) if solid. Then the tube was degassed and filled with N 2. Dioxane (1 ml), 1 M KH (4 μl) and aryl bromide if liquid were added in order. The tube was sealed and stirred at 25 o C for 6 h. The mixture was transferred to a flask containing Et 2 (1 ml) and H 2 (1 ml). After stirring for 15 minutes, the organic layer was separated and the aqueous was extracted by Et 2 (1 ml 2). The combined organic layer was washed with saturated brine (5 ml 2) and dried over anhydrous Na 2 S 4. After filtration, the solvent was evaporated off and crude benzylboronate was obtained. Step 2: a modified Schlenk tube was charged with Pd 2 (dba) 3 (9 mg,.1 mmol), PPh 3 (52 mg,.2 mmol), Ag 2 (7 mg,.3 mmol) and aryl iodide if solid. Then the tube was degassed and filled with N 2. Aryl iodide was added if liquid. Then a solution of crude benzylboronate in dioxane (1 ml) was added. The tube was sealed and stirred at 9 o C for 24 h. After cooled to room temperature, the mixture was filtrated through a pad of silica gel and washed with Et 2. Then the solvent was evaporated in vacuum, and the product was purified by silica gel chromatography. 5. General procedure for allylboration of 2r with aldehyde S5

6 A microwave tube was charged with 2r (.2 mmol), followed by degassing and back filling with N 2. Then heptanal (56 μl,.4 mmol, 2 equiv) and toluene (1 ml) was added. The tube was sealed and heated at 11 o C for 24 h. After cooled to room temperature, saturated NH 4 Cl (2 ml) was added Product was extracted by Et 2 (5 ml 3). The combined organic solution was washed with saturated brine (1 ml) and dried over anhydrous Na 2 S 4. After the solvent was evaporated off, the crude product was purified by silica gel chromatography. 6. Spectra data 6.1 Spectra data of 1,1-diboronates 2,2'-(3-Phenylpropane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxa borolane) (2a) White solid (322 mg, 86%). 2 Mp: o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.3; elute solution ( PE/EA, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 5H), 2.59 (t, J = 8. Hz, 2H), (m, 2H), 1.24 (s, 12H), 1.23 (s, 12H),.81 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ , , 128.9, , 82.96, 38.7, 27.98, 24.9, ,2'-(3-(4-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetrameth yl-1,3,2-dioxaborolane) (2b) White solid (322 mg, 71%). Mp: o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.31; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.35 (d, J = 8.3 Hz, 1H), 7.4 (d, J = 8.3 Hz, 1H), 2.54 (t, J = 7.8 Hz, 2H), (m, 2H), 1.23 (s, 12H), 1.22 (s, 12H),.77 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ , , 13.35, , 83.2, 37.99, 27.75, 24.88, 24.5; HRMS (ESI, m/z): [M+H] + calcd for C 21 H 34 BrB 2 4, ; found, ; LRMS (EI, m/z): 45 (2), 435 (8), 35 (1), 11 (22), 278 (56), 84 (1); IR (film): 2977, 2931, 2863, 1314, 1139 cm -1. 2,2'-(2-methylpropane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaboro lane) (2c) White solid (26 mg, 84%). Mp: o B C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.2; elute solution (petroleum ether : ethyl acetate, B 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 2.4 (m, 2H), 1.23 (s, 12H), c (s, 12H),.96 (d, J = 6.6 Hz, 1H),.6 (d, J = 1.1 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.78, 26.48, 25.37, 24.86, 24.49; HRMS (ESI, m/z): [M+H] + calcd for C 16 H 33 B 2 4, ; found, ; LRMS (EI, m/z): 31 (1), 295 (19), 21 (6), 195 (4), 84 (1); IR (film): 2979, 2867, 136, 1142 cm -1. S6

7 2,2'-(2,2-dimethylpropane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxa borolane) (2d) White solid (167 mg, 52%). Mp: o B C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.29; elute solution (petroleum ether : ethyl acetate, B 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 1.23 (s, 12H), 1.22 (s, 12H), 2d 1.6 (s, 9H),.77 (s, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.57, 31.85, 31.28, 24.89, 24.5,; HRMS (ESI, m/z): [M+H] + calcd for C 17 H 35 B 2 4, ; found, ; LRMS (EI, m/z): 324 (1), 39 (43), 224 (13), 83 (1); IR (film): 2978, 2866, 1317, 114 cm -1. 2,2'-(cyclohexylmethylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborola ne) (2e) White solid (299 mg, 85%). Mp: o B C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.31; elute solution (petroleum ether : ethyl B acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 6H), 2e (m, 27H), (m, 2H),.64 (d, J = 1.1 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.76, 35.96, 35.88,26.73, 26.28, 24.84, 24.53; HRMS (ESI, m/z): [M+H] + calcd for C 19 H 37 B 2 4, ; found, ; LRMS (EI, m/z): 35 (1), 335 (16), 268 (45), 25 (7), 166 (31), 84 (1); IR (film): 2977, 2922, 2851, 1315, 114 cm -1. 2,2'-(cyclopropylmethylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborola ne) (2f) White solid (113 mg, 37%). Mp: o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.23; elute solution ( P petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 1.24 (s, 12H), 1.23 (s, 12H), (m, 1H),.44 (m, 2H),.29 (d, J = 9.2 Hz, 1H), (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.93, 24.78, 24.52, 7.22, 5.78; HRMS (ESI, m/z): [M+H] + calcd for C 16 H 31 B 2 4, ; found, ; LRMS (EI, m/z): 38 (1), 293 (3), 28 (7), 84 (1); IR (film): 373, 2978, 1316, 1141 cm -1. 2,2'-(undec-1-ene-1,1-diyl)bis(4,4,5,5-tetramethyl-1, 3,2-dioxaborolane) (2g) B Colorless oil (287 mg, 71%). TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.31; elute solution B (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR 2g (4 MHz, CDCl 3 ) δ (m, 1H), 4.98 (d, J = 17.1 Hz, 1H), 4.92 (d, J = 1.1 Hz, 1H), (m, 2H), (m, 2H), (m, 36H),.71 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ , 114.2, 82.83, 33.82, 32.55, 29.57, 29.45, 29.42, 29.12, 28.96, 25.66, 24.84, 24.5,; HRMS (ESI, m/z): [M+H] + calcd for C 23 H 45 B 2 4, ; found, 47.35; LRMS (EI, m/z): 46 (1), 391 (17), 36 (2), 84 (1); IR (film): 376, 2978, 2926, 2855,1312, 1141 cm -1. S7

8 B 2,2'-(3-(2-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetrameth yl-1,3,2-dioxaborolane) (2h) White solid (327 mg, 72%). Mp: 8-82 o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.2; elute solution (petroleum ether : B ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.48 (d, J Br 2h = 8. Hz, 1H), (m, 2H), 7. (m, 1H), 2.72 (t, J = 8.2 Hz, 2H), 2.54 (t, J = 7.8 Hz, 2H), (m, 2H), 1.24 (s, 12H), 1.24 (s, 12H),.84 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ , , 13.54, 127.2, , 124.4, 83.3, 38.64, 26.21, 24.92, 24.53; HRMS (ESI, m/z): [M+H] + calcd for C 21 H 34 BrB 2 4, ; found, ; LRMS (EI, m/z): 45 (1), 435 (12), 278 (8), 83 (1); IR (film): 2977, 2932, 2866, 1315, 1139 cm morpholino-4,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborola n-2-yl)butan-1-one (2i) B White solid (27 mg, 66%). Mp: o C; TLC (petroleum N ether : ethyl acetate, 1:1 v/v) R f =.21; elute solution B (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, 2i CDCl 3 ) δ (m, 4H), (m, 4H), 2.34 (t, J = 8.2 Hz, 2H), (m, 2H), 1.23 (s, 12H), 1.22 (s, 12H),.75 (t, J = 7.4 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 172.5, 83.8, 66.94, 66.82, , 41.74, 35.94, 24.9, 24.46, 22.; HRMS (ESI, m/z): [M+H] + calcd for C 2 H 38 B 2 N 6, ; found, ; LRMS (EI, m/z): 49 (36), 394 (24), 351 (98), 39 (28), 129 (1), 83 (7); IR (film): 2977, 292, 2851, 1645, 1314, 1139 cm (3-(4,4,5,5-tetramethyl-1,2-oxaborolan-2-yl)-3-(4,4,5,5-tetra methyl-1,3,2-dioxaborolan-2-yl)propyl)isoindoline-1,3-dione (2j) B White solid (315 mg, 71%). Mp: o C; TLC (petroleum N B ether : ethyl acetate, 5:1 v/v) R f =.38; elute solution (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 2j (m, 2H), (m, 2H), 3.7 (t, J = 7.1 Hz, 2H), (m, 2H), 1.24 (s, 12H), 1.23 (s, 12H),.75 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ , 133.6, , , 83.13, 39.58, 24.83, 24.59, 24.42; HRMS (ESI, m/z): [M+H] + calcd for C 23 H 34 B 2 N 6, ; found, ; LRMS (EI, m/z): 441 (6), 426 (8), 383 (1), 341 (45), 241 (47), 13 (7), 84 (41); IR (film): 2978, 2934, 1714, 1322, 114 cm -1. 2,2'-(cyclopentane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2k) White solid (14 mg, 44%). Mp: o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.46; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 1.8 (t, J = 6.8 Hz, 4H), (m, 4H), 1.21 (s, 24H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.86, 3.55, 27.27, S8

9 24.57; HRMS (ESI, m/z): [M+H] + calcd for C 17 H 33 B 2 4, ; found, ; LRMS (EI, m/z): 322 (1), 37 (9), 265 (1), 222 (4), 27 (17), 84 (1); IR (film): 2977, 2945, 2866, 1371, 1337, 114, 1299, 1135 cm -1. 2l B B 2,2'-(cycloheptane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2l) White solid (168 mg, 48%). Mp: o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.53; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 4H), (m, 4H), (m, 4H), 1.22 (s, 24H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.76, 31.67, 28.94, 27.87, 24.63; HRMS (ESI, m/z): [M+H] + calcd for C 19 H 37 B 2 4, ; found, ; LRMS (EI, m/z): 35 (1), 335 (1), 293 (1), 25 (5), 235 (11), 84 (1); IR (film): 2978, 2923, 2853, 137, 131, 1298, 1137 cm -1. B B 2m 2,2'-(cyclohexane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2m) White solid (137 mg, 41%). Mp: 59-6 o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.5; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 4H), (m, 6H), 1.22 (s, 24H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.74, 29.53, 26.74, 26.43, 24.63; HRMS (ESI, m/z): [M+H] + calcd for C 18 H 35 B 2 4, ; found, ; LRMS (EI, m/z): 336 (1), 321 (7), 236 (2), 84 (1); IR (film): 2978, 2925, 2849, 137, 1317, 1298, 1148, 113 cm -1. B B 2,2'-(4-(tert-butyl)cyclohexane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2n) White solid (262 mg, 67%). Mp: o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.39; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 2.7 (d, J = 13. Hz, 2H), 1.69 (d, J = 1.5 Hz, 2H), (m, 2H), 1.24 (s, 12H), 1.19 (s, 12H), (m, 3H),.8 (s, 9H); 13 C NMR (1 MHz, CDCl 3 ) δ 82.83, 82.66, 48., 32.54, 29.96, 27.4, 27.6, 24.61; HRMS (ESI, m/z): [M+H] + calcd for C 22 H 43 B 2 4, ; found, ; LRMS (EI, m/z): 392 (1), 377 (7), 292 (1), 84 (1); IR (film): 2976, 2934, 2854, 134, 114 cm -1. 2n N 2o B B tert-butyl 4,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)piperidine-1-carboxylate (2o) White solid (217 mg, 5%). Mp: o C; TLC (petroleum ether : ethyl acetate, 5:1 v/v) R f =.47; elute solution (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 1.44 (s, 9H) 1.22 (s, 24H); 13 C NMR (1 MHz, CDCl 3 ) δ , 83.15, 78.85, 28.45, 24.62; HRMS (ESI, m/z): [M+H] + calcd for C 22 H 42 B 2 N 6, ; found, ; LRMS (EI, m/z): 437 (3), 38 S9

10 (3), 364 (18), 336 (1), 84 (8); IR (film): 2978, 2933, 285, 1691, 1364, 1322, 135, 1299,1141, 1126 cm -1. 2,2'-(1,2,3,4-tetrahydronaphthalene-1,1-diyl)bis(4,4,5,5-tetramethyl-1, 3,2-dioxaborolane) (2p) White solid (88 mg, 23%). 3 Mp: 1-11 o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.44; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.37 (d, J = 7.7 Hz, 1H), (m, 1H), (m, 2H), 2.73 (t, J = 6.4 Hz, 1H), (m, 2H), (m, 2H), 1.2 (s, 12H), 1.2 (s, 12H); 13 C NMR (1 MHz, CDCl 3 ) δ , 135.7, 13.48, , , , 83.18, 3.26, 27.76, 24.66, 24.49, 23.2; HRMS (ESI, m/z): [M+H] + calcd for C 22 H 34 B 2 Na 4, ; found, ; LRMS (EI, m/z): 384 (2), 321 (7), 236 (2), 84 (1); IR (film): 2977, 2926, 2864, 1343, 1315, 1138 cm -1. B B 2q 2,2'-(chroman-4,4-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2q) White solid (13 mg, 34%). Mp: o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.24; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.39 (dd, J = 1.6 Hz, J = 7.8 Hz, 1H), (m, 1H), (m, 1H), 6.73 (dd, J = 1.2 Hz, J = 8.1 Hz, 1H), (m, 2H), (m, 2H), 1.21 (s, 24H); 13 C NMR (1 MHz, CDCl 3 ) δ , 13.97, , 124.1, , 116.4, 83.53, 66.4, 26.66, 24.66, 24.48; HRMS (ESI, m/z): [M+H] + calcd for C 21 H 33 B 2 5, ; found, ; LRMS (EI, m/z): 386 (13), 371 (1), 343 (1), 329 (15), 286 (5), 23 (1), 83 (55); IR (film): 2982, 2917, 2849, 1318, 1136 cm -1. B B 2r 2,2'-(3-methylcyclohex-2-ene-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dio xaborolane) (2r) White solid (171 mg, 49%). Mp: 59-6 o C; TLC (petroleum ether : ethyl acetate, 2:1 v/v ) R f =.43; elute solution (petroleum ether : ethyl acetate, 5:1 v/v ). 1 H NMR (4 MHz, CDCl 3 ) δ 5.54 (s, 1H), 1.83 (t, J = 6. Hz, 1H), (m, 7H), 1.22 (s, 12H, )1.21 (s, 12H); 13 C NMR (1 MHz, CDCl 3 ) δ , , 82.96, 29.82, 25.78, 24.77, 24.42, 23.14; HRMS (ESI, m/z): [M+Na] + calcd for C 19 H 34 B 2 Na 4, ; found, ; LRMS (EI, m/z): 348 (8), 333 (4), 248 (5), 83 (1); IR (film): 2978, 2926, 2864, 1343, 1315, 1138 cm (3,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propy l)aniline (2t) White solid (228 mg, 59%). Mp: o C; TLC (petroleum ether : ethyl acetate, 3:1 v/v) R f =.22; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 6.96 (d, J = 8.1 Hz, 2H), 6.59 (d, J = 8.1 Hz, 2H), 3.51 (s, 2H, NH 2 ), 2.47 (t, J = 8. Hz, 2H), (m, 2H), S1

11 1.23 (s, 12H), 1.22 (s, 12H),.79 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ , , , 115.9, 82.88, 37.84, 28.24, 24.86, 24.48; HRMS (ESI, m/z): [M+H] + calcd for C 21 H 36 B 2 N 4, ; found, ; LRMS (EI, m/z): 387 (6), 372 (1), 287 (1), 16 (1), 83 (1); IR (film): 337, 2978, 2931, 2859, 1314, 1138 cm -1. (4-(3,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pr opyl)phenyl)methanol (2v) White solid (321 mg, 8%). Mp: 9-92 o C; TLC (petroleum ether : ethyl acetate, 3:1 v/v) R f =.22; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.24 (d, J = 7.5 Hz, 2H), 7.17 (d, J = 7.6 Hz, 2H), 4.62 (s, 2H), 2.48 (t, J = 8. Hz, 2H), (m, 2H), 1.77 (br, 1H, H), 1.23 (s, 12H), 1.23 (s, 12H),.8 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ , 138.6, , , 82.95, 65.25, 38.3, 27.92, 24.86, 24.46; HRMS (ESI, m/z): [M+Na] + calcd for C 22 H 36 B 2 Na 5, ; found, ; LRMS (EI, m/z): 399 (14), 346 (1), 32 (33), 258 (7), 84 (1); IR (film): 3462, 2978, 2931, 2865, 1315, 1138 cm (3,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pro pyl)benzaldehyde (2w) White solid (162 mg, 81%). Mp: o C; TLC (petroleum B ether : ethyl acetate, 5:1 v/v) R f =.39; elute solution B (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 HC 2w MHz, CDCl 3 ) δ 9.96 (s, 1H), 7.77 (d, J = 8.1 Hz, 2H), 7.34 (d, J = 8. Hz, 2H), 2.67 (t, J = 8. Hz, 2H), (m, 2H), 1.24 (s, 12H), 1.24 (s, 12H),.8 (t, J = 7.8 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 192.3, 15.5, , , , 83.5, 38.78, 27.52, 24.86, 24.46; HRMS (ESI, m/z): [M+Na] + calcd for C 22 H 34 B 2 Na 5, ; found, ; LRMS (EI, m/z): 4 (6), 385 (13), 3 (4), 228 (1), 272 (6), 216 (4), 84 (95); IR (film): 2979, 2933, 2866, 171, 1316, 1138 cm Spectra data of 1-silyl-1-boron compounds dimethyl(phenyl)(3-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxabo rolan-2-yl)propyl)silane (3a) Colorless oil (158 mg, 83%). 4 TLC (petroleum ether : ethyl acetate, 6:1 v/v) R f =.32; elute solution (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), (m, 2H), (m, 3H), 2.68 (ddd, J = 4.8 Hz, J = 9.6 Hz, J = 13.6 Hz, 1H), 2.44 (ddd, J = 6.9 Hz, J = 9.7 Hz, J = 13.4 Hz, 1H), (m, 1H), (m, 1H), 1.22 (s, 6H), 1.18 (s, 6H),.7 (dd, J = 2.9 Hz, J = 12. Hz, 1H),.3 (s, 3H),.29 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ , , , , , , , , 82.81, 39.44, 28.3, 25.18, 24.71, -2.29, S11

12 methyl 4-(3-(dimethyl(phenyl)silyl)-3-(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl)propyl)benzoate (3b) Colorless oil (157 mg, 72%). TLC (petroleum ether : ethyl acetate, 1:1 v/v) R f =.47; elute solution (petroleum ether : ethyl acetate, 2:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.9 (d, J = 8.2 Hz, 2H), (m, 2H), (m, 3H), 7.14 (d, J = 8.2 Hz, 2H), 3.89 (s, 3H), 2.73 (ddd, J = 5.2 Hz, J = 9.2 Hz, J = 13.6 Hz, 1H), 2.49 (ddd, J = 7.1 Hz, J = 9.4 Hz, J = 13.4 Hz, 1H), (m, 1H), (m, 1H), 1.22 (s, 6H), 1.19 (s, 6H),.67 (dd, J = 3. Hz, J = 12. Hz, 1H),.31 (s, 3H),.29 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 167.2, , 138.6, , , , , , 82.88, 51.9, 39.29, 29.68, 27.64, 25.17, 24.72, -2.3, -3.46; HRMS (ESI, m/z): [M+Na] + calcd for C 25 H 35 BNa 4 Si, ; found, ; LRMS (EI, m/z): 423 (2), 47 (3), 36 (4), 339 (5), 189 (4), 147 (17), 135 (1), 118 (5); IR (film): 2978, 2917, 2849, 172, 1353, 128, 1143, 1112 cm -1. dimethyl(3-(4-nitrophenyl)-1-(4,4,5,5-tetramethyl-1,3,2-dio xaborolan-2-yl)propyl)(phenyl)silane (3c) Pale yellow oil (157 mg, 74%). TLC (petroleum ether : ethyl acetate, 2:1 v/v) R f =.27; elute solution (petroleum ether : ethyl acetate, 5:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 8.8 (d, J = 8.7 Hz, 2H), (m, 2H), (m, 3H), 7.2 (d, J = 8.6 Hz, 2H), 2.77 (ddd, J = 5., 9.3, 13.7 Hz, 1H), 2.53 (ddd, J = 7.2, 9.3, 13.5 Hz, 1H), (m, 1H), (m, 1H), 1.23 (s, 6H), 1.2 (s, 6H),.65 (dd, J = 3., 12. Hz, 1H),.32 (s, 3H),.3 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 15.46, 146.2, 138.4, , , , , , 82.99, 39.5, 27.56, 25.18, 24.73, -2.3, -3.58; HRMS (ESI, m/z): [M+Na] + calcd for C 23 H 32 BNNa 4 Si, ; found, ; LRMS (EI, m/z): 41 (3), 347 (2), 326 (2), 289 (17), 271 (16), 189 (3), 135 (1); IR (film): 2977, 2931, 286, 1519, 1345, 1143, 1111 cm -1. (3-(4-bromophenyl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborol an-2-yl)propyl)dimethyl(phenyl)silane (3d) Colorless oil (179 mg, 78%). TLC (petroleum ether : ethyl acetate, 6:1 v/v) R f =.29; elute solution (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 2H), (m, 5H), 6.95 (d, J = 8.3 Hz, 2H), 2.62 (ddd, J = 4.8, 9.1, 13.7 Hz, 1H), 2.39 (ddd, J = 7.1, 9.3, 13.4 Hz, 1H), (m, 1H), (m, 1H), 1.21 (s, 6H), 1.18 (s, 6H),.65 (dd, J = 2.9, 12. Hz, 1H),.3 (s, 3H),.29 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ , , , , 13.3, , 127.6, , 82.86, 38.66, 27.81, 25.17, 24.72, -2.29, -3.46; HRMS (ESI, m/z): [M+Na] + calcd for C 23 H 32 BBrNa 2 Si, ; found, ; LRMS (EI, m/z): 445 (1), 382 (2), 289 (14), 235 (11), 189 (55), 135 (1); IR (film): 2977, 293, 2858, 1352, 1143 cm -1. S12

13 (cyclohexyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)dim ethyl(phenyl)silane (3e) Colorless oil (96 mg, 54%). TLC (petroleum ether : ethyl acetate, 6:1 v/v) R f =.29; elute solution (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), (m, 6H), (m, 16H), (m, 1H),.67 (d, J = 7.8 Hz, 1H),.34 (s, 3H),.32 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 14.27, , , , 82.6, 36.72, 35.5, 26.83, 26.18, 25.16, 24.95, -1.26, -1.32; HRMS (ESI, m/z): [M+Na] + calcd for C 21 H 35 BNa 2 Si, ; found, ; LRMS (EI, m/z): 343 (5), 31 (3), 259 (15), 179 (25), 163 (55), 135 (1); IR (film): 2978, 2924, 2851, 1371, 1339, 132, 1145, 1111 cm -1. dimethyl(2-methyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pro pyl)(phenyl)silane (3f) Colorless oil (72 mg, 45%). 4 TLC (petroleum ether : ethyl acetate, 6:1 v/v) R f =.29; elute solution (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), (m, 1H), 1.19 (s, 6H), 1.14 (s, 6H),.98 (d, J = 6.7 Hz, 1H),.88 (d, J = 6.7 Hz, 1H),.65 (d, J = 7.4 Hz, 1H),.35 (s, 3H),.33 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 14.3, , , 127.5, 82.59, 27.2, 26.43, 25.17, 24.9, 24.83, -1.33, Spectra data of diarylmethanes derivatives propane-1,1,3-triyltribenzene (5a) Colorless oil (27.6 mg, 51%). 5 TLC (petroleum ether : ethyl acetate, 6:1 v/v) R f =.38; elute solution (petroleum ether ). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 1H), (m, 5H), 3.91 (t, J = 7.7 Hz, 1H), 2.57 (t, J = 7.8 Hz, 2H), (m, 2H); 13 C NMR 5a (1 MHz, CDCl 3 ) δ 144.8, 142.8, , , , , , , 5.66, 37.3, methyl 4-(1,3-diphenylpropyl)benzoate (5b) Pale yellow oil (31.5 mg, 48%). TLC (petroleum ether : ethyl acetate, 3:1 v/v) R f =.23; elute solution (petroleum ether : ethyl acetate, 1:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.96 (d, J = 8.3 Hz, 2H), (m, 1H), 7.12 (d, J = 7.3 Hz, 2H), 3.97 (t, J = 7.7 Hz, 1H), 3.88 (s, 3H), 2.57 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ , 15.17, , 141.7, , 128.6, , , , 127.9, , , , 51.97, 5.59, 37.1, 33.92; HRMS (ESI, m/z): [M+H] + calcd for C 23 H 23 2, ; found, ; LRMS (EI, m/z): 33 (34), 239 (2), 225 (1), 165 (43), 15 (19); IR (film): 362, 327, 2948, 172, 161, 1495, 1453, 128, 119 cm -1. S13

14 (1-(4-methoxyphenyl)propane-1,3-diyl)dibenzene (5c) Colorless oil (26.3 mg, 44%). TLC (petroleum ether : ethyl acetate, 6:1 v/v) R f =.28; elute solution (petroleum ether : ethyl acetate, 2:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 6H), (m, 6H), 6.82 (d, J = 8.7 Hz, 2H), Me 5c 3.86 (t, J = 7.7 Hz, 1H), 3.76 (s, 3H), 2.56 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ , , , , , , 128.3, , 126.4, , , 55.18, 49.78, 37.47, 34.9; HRMS (EI, m/z): M + calcd for C 22 H 22, ; found ; LRMS (EI, m/z): 32 (17), 197 (1), 165 (1), 153 (9); IR (film): 362, 327, 2932, 169, 1511, 1453, 1248, 136 cm -1. methyl 4-(1-(4-fluorophenyl)-3-phenylpropyl)benzoate F (5d) 5d C 2 Me Pale yellow oil (26. mg, 37%). TLC (petroleum ether : ethyl acetate, 3:1 v/v) R f =.25; elute solution (petroleum ether : ethyl acetate, 6:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 7.96 (d, J = 8.2 Hz, 2H), (m, 4H), (m, 3H), 7.11 (d, J = 7.3 Hz, 2H), (m, 2H), 3.95 (t, J = 7.7 Hz, 1H), 3.89 (s, 3H), 2.56 (t, J = 7.8 Hz, 2H), (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ 166.9, (d, J = Hz, 1C), 149.9, , (d, J = 3.3 Hz, 1C), , (d, J = 7.9 Hz, 1C), , , , 127.8, , (d, J = 21.1 Hz, 1C), 52.1, 49.74, 37.12, 33.84; HRMS (ESI, m/z): [M+H] + calcd for C 23 H 22 F 2, ; found, ; LRMS (EI, m/z): 348 (22), 243 (1), 183 (3), 15 (18); IR (film): 327, 2948, 2861, 172, 169, 158, 1435, 128, 111 cm methoxy-4-(3-phenyl-1-(p-tolyl)propyl)benzene (5e) Me Colorless oil (32.9 mg, 52%). TLC (petroleum ether : ethyl 5e Me acetate, 6:1 v/v) R f =.34; elute solution (petroleum ether : ethyl acetate, 2:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ (m, 11H), 6.81 (d, J = 8.6 Hz, 2H), 3.83 (t, J = 7.7 Hz, 1H), 3.75 (s, 3H), 2.57 (t, J = 7.6 Hz, 2H), 2.56 (t, J = 7.8 Hz, 2H), (m, 2H), 2.29 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ , 142.2, , , , , , , , , , 77.32, 55.17, 49.36, 37.49, 34.1, 2.95; HRMS (MALDI, m/z): [M+Na] + calcd for C 23 H 24 Na, ; found ; LRMS (EI, m/z): 316 (11), 277 (21), 211 (1), 165 (6), 153 (8); IR (film): 325, 2925, 2858, 168, 151, 1454, 1247, 136 cm -1. S14

15 6.4 Spectra data of 6. 1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- H yl)cyclohex-2-en-1-yl)heptan-1-ol (6) B Colorless oil (49 mg, 73%). TLC (petroleum ether : ethyl acetate, 1:1 v/v) R f =.33 ; elute solution (petroleum 6 ether : ethyl acetate, 2:1 v/v). 1 H NMR (4 MHz, CDCl 3 ) δ 6.22 (s, 1H), 3.35 (d, J = 8.6 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), 1.46 (s, 1H, H), (m, 22H),.95 (s, 3H),.88 (t, J = 6.5 Hz, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ , 83.13, 78.5, 4.82, 31.89, 3.35, 29.38, 29.11, 27.2, 26.36, 24.85, 24.74, 23.25, 22.65, 19.19, 14.9; HRMS (EI, m/z): M + calcd for C 2 H 37 B 3, ; found ; LRMS (EI, m/z): 321 (5), 222 (8), 165 (52), 122 (33), 11 (97), 94 (1), 85 (72); IR (film): 3447, 2928, 2858, 1628, 1459, 1385, 1371, 1325, 1297, 1145 cm References (1) Suginome, M.; Matsuda, T.; Ito, Y. rganometallics 2, 19, (2) Li, H.; Wang, L.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 212, 51, (3) Abu Ali, H.; Goldberg, I.; Kaufmann, D.; Burmeister, C.; Srebnik, M. rganometallics 22, 21, 187. (4) Aggarwal, V. K.; Binanzer, M.; de Ceglie, M. C.; Gallanti, M.; Glasspoole, B. W.; Kendrick, S. J. F.; Sonawane, R. P.; Vázquez-Romero, A.; Webster, M. P. rg. Lett. 211, 13, 149. (5) Giese, B.; Thoma, G. Helcetic Chimica Acta 1991, 74, S15

16 8. 1 H and 13 C Spectra 8.1 Spectra of 1,1-diboronates B B 2a B B 2a S16

17 S

18 S

19 S19

20 S

21 S

22 S B B 2g

23 S

24 S

25 S

26 S26

27 S27

28 S

29 S

30 S

31 S

32 S

33 S

34 S

35 S

36 S

37 S Spectra of 1-silyl-1-boron compounds

38 S

39 S

40 S

41 S41

42 S

43 S

44 S

45 S

46 S

47 S

48 S Spectra of diarylmethanes derivatives

49 S

50 S

51 S

52 S

53 S Spectra of

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