copper-catalyzed propargylation of diborylmethane · copper-catalyzed propargylation of...

Supporting Information

Copper-Catalyzed Propargylation of DiborylmethaneFeng Li, Zhen-Qi Zhang, Xi Lu, Bin Xiao,*Yao Fu*

Hefei National Laboratory for Physical Sciences at the Microscale, iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of Biomass Clean Energy, University of Science and Technology of China, Hefei

230026, China.

Table of Contents

I. General Information……………………..……………………………P2

II. Preparation of Substrates…………………………………………P3-P4

III. Copper-Catalyzed Propargylation of Diborylmethane….…P5-P17

IV. References……………….………………….…………………………………P18

V. Spectral data…………………………....…………………………………P19-P70

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Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2017


I. General Informationa. Materials All reactions were carried out in oven-dried Schlenk tubes under an argon or nitrogen

atmosphere (purity ≥99.999%). The following chemicals were purchased and used as

received: LiOtBu (J&K), LiOMe (J&K). Anhydrous THF (Acros), anhydrous Toluene

(Acros), anhydrous Dioxane (Acros), anhydrous DMSO (Acros), and anhydrous

CH3CN (Acros), and Dibromomethane-d2 (Aldrich) were stored over 4 Å molecular

sieves under an argon atmosphere in a septum-capped bottle. All other reagents and

solvents mentioned in this text were purchased from commercial sources and used

without purification.

b. Analytical Methods1H, 11B and 13C spectra were recorded either on Bruker Avance 400 or Varian

Mercury 400 spectrometer at ambient temperature in CDCl3 unless otherwise noted;

11B NMR signals are quoted relative to BF3Et2O. Data for 1H-NMR are reported as

follows: chemical shift (δ ppm), multiplicity, integration, and coupling constant (Hz).

Data for 13C-NMR are reported in terms of chemical shift (δ ppm), multiplicity, and

coupling constant (Hz). Gas chromatographic (GC) analysis was acquired on a

Shimadzu GC-2014 Series GC System equipped with a flame-ionization detector.

GC-MS analysis was performed either on Thermo Scientific AS 3000 Series GC-MS

System or Agilent 6890N gas chromatograph coupled to an Agilent 5973 inert mass

selective detector. HRMS analysis was performed on Finnigan LCQ advantage Max

Series MS System. Elementary Analysis was carried out on Elementar Vario EL III

elemental analyzer.

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II. Preparation of Substrates

a. Preparation of propargyl phosphates

Propargyl phosphates were prepared according to literature procedure. [1]

A 50 mL round-bottom flask charged with anhydrous CH2Cl2 (15 mL), propargy

alcohol (10 mmol) and pyridine (2.5 equiv), DMAP (N, N-dimethyl-4-aminopyridine,

10 mol %) was added,and the mixture was cooled with an ice bath. To the solution,

diethylchlorophosphate (12 mmol, 1.1 equiv) was added dropwise and the mixture

was stirred at 0 ºC for 10 min. The mixture was allowed to warm up to room

temperature and stirred overnight at room temperature. The resulting mixture was

diluted with DCM (15 mL) and washed with water (10 mL ×2). The organic layer was

dried over MgSO4. After filtration and removal of the solvents in vacuo, distillation

gave propargyl phosphates.

b. Preparation of propargyl chlorides

A 50 mL round-bottom flask charged with anhydrous CH2Cl2 (15 mL), propargy

alcohol (10 mmol) and Pyridine (1.2 equiv), and the mixture was cooled with an ice

bath. To the solution, SOCl2 (12 mmol, 1.1 equiv) was added dropwise and the

mixture was stirred at 0 ºC for 10 min. The mixture was allowed to warm up to room

temperature and stirred overnight at room temperature. The resulting mixture was

diluted with ether (20 mL) and washed with 1N HCl solution (15 mL × 3). The water

layer was extracted with Et2O (20 mL × 3). The combined organic extracts were

washed with saturated NaHCO3 aq. (15 mL × 3). The organic layer was dried over

MgSO4. After filtration and removal of the solvents in vacuo, distillation gave

propargyl chlorides.

c. Preparation of mono- and di-deuterated gem-diborylalkanes

1, 1-Diborylalkanes were prepared according to literature procedure. [2]

Method A. In air, CuI (10 mmol, 1900 mg), MeOLi (30 mmol, 1140 mg), and

diboron reagent (22 mmol, 5588 mg) were added to a Schlenk tube equipped with a

stir bar. The vessel was evacuated and filled with argon (three cycles). DMF (60 mL),

and Dibromomethane (10mmol, 1740 mg) were added via syringe under an argon

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atmosphere. The reaction mixture was stirred at 40 oC for 24 h, and then diluted with

EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc),

concentrated, and purified by column chromatography, 1, 1-Diborylalkane (1) was

obtained.

Method B. In air, Cu-catalyst (10 mmol, 1900 mg), MeOLi (30 mmol, 1140 mg), and

diboron reagent (22 mmol, 5588 mg) were added to a Schlenk tube equipped with a

stir bar. The vessel was evacuated and filled with argon (three cycles). DMF (60 mL),

and Dibromomethane-d2 (10mmol, 1760 mg) were added via syringe under an argon

atmosphere. The reaction mixture was stirred at 40 oC for 24 h, and then diluted with

EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc),

concentrated, and purified by column chromatography, di-deuterated gem-

diborylalkanes (2) was obtained.

B

BDD

OO

OO

Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methane-d2 (2).

Following general procedure C, 1 was used, the product was isolated by flash

chromatography (1% ethyl acetate/hexane) as white solid, (1890 mg, 70%).

1H NMR (400 MHz, CDCl3) δ 1.23 (s, 24H).

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III. Copper-Catalyzed Propargylation Reaction of

Diborylmethane

Experimental Procedures for Examples Described in Table 1.

In air, Cu-catalyst, base, ligand, were added to a Schlenk tube equipped with a stir bar.

The vessel was evacuated and filled with argon (three cycles). Solvent (1.0 mL) was

added in turn by syringe under argon atmosphere at room temperature, and then

stirred at 60 oC for 10 min. Then diborylmethane was added in turn under an argon

atmosphere and stirred at 60 oC for 10 min. And propargyl phosphates were added in

turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h,

then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or

EtOAc), and Triphenylmethane (36.6 mg, 0.15 mmol) was added as internal standard.

The product yield was determined by GC.

B O

O

4,4,5,5-tetramethyl-2-(4-phenylbut-3-yn-1-yl)-1,3,2-dioxaborolane (1b).Following general procedure A, 1a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil, (43mg, 83%).1H NMR (400 MHz, CDCl3) δ 7.34 – 7.25 (m, 2H), 7.23 – 7.12 (m, 3H), 2.44 (t, J = 7.6 Hz, 2H), 1.19 (s, 12H), 1.07 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 131.68, 128.31, 127.55, 124.38, 92.11, 83.50, 80.05, 25.01, 14.34.11B NMR (128 MHz, CDCl3) δ 33.49.HRMS (APCI) calcd for C16H2O2B+ [(M+H)+]: 257.1707; found: 257.1709.

Experimental Procedures for Examples Described in Table2.General Procedure A. In air, CuI 10 mol%, t-BuOLi 3 equiv, PPh3 20 mol%, were

added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled

with argon (three cycles). THF (1.0 mL) was added in turn by syringe under argon

atmosphere at room temperature, and then stirred at 60 oC for 10 min. Then

diborylmethane (1) was added in turn under an argon atmosphere and stirred at 60 oC

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for 10 min. And propargyl phosphates (0.2 mmol) were added in turn under an argon

atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture

was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O

or EtOAc), concentrated, and purified by column chromatography.

B O

O

O

2-(4-(4-methoxyphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2b).Following general procedure A, 2a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil, (36mg, 62%).1H NMR (400 MHz, CDCl3) δ 7.17 (t, J = 7.9 Hz, 1H), 6.97 (d, J = 7.5 Hz, 1H), 6.91 (s, 1H), 6.81 (dd, J = 8.3, 2.0 Hz, 1H), 3.78 (s, 3H), 2.51 (t, J = 7.6 Hz, 2H), 1.26 (s, 12H), 1.14 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 159.40, 129.37, 125.41, 124.28, 116.51, 114.25, 92.03, 83.54, 80.00, 55.41, 29.54, 25.03, 14.35.11B NMR (128 MHz, CDCl3) δ 33.53.HRMS (APCI) calcd for C16H22O2B+ [(M+H)+]: 287.1813; found: 287.1815

B O

O

O

2-(4-(4-methoxyphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3b).Following general procedure A, 3a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil, (40mg, 70%).1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.6 Hz, 2H), 6.79(d, J = 8.6 Hz, 2H), 3.78(s, 3H), 2.49 (t, J = 7.6 Hz, 2H), 1.25 (s, 12H), 1.13 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 159.08, 133.01, 116.58, 113.93, 90.46, 83.49, 79.76, 55.43, 25.02, 14.34. 11B NMR (128 MHz, CDCl3) δ 33.53.HRMS (APCI) calcd for C16H22O2B+ [(M+H)+]: 287.1813; found: 287.1813.

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B O

O

O

2-(4-(4-ethoxyphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4b).Following general procedure A, 4a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil, (41mg, 68%).1H NMR (400 MHz, CDCl3) δ 7.34 – 7.18 (m, 2H), 6.76 (d, J = 8.7 Hz, 2H), 3.99 (q, J = 7.0 Hz, 2H), 2.47 (t, J = 7.6 Hz, 2H), 1.38 (t, J = 7.0 Hz, 3H), 1.24 (s, 12H), 1.11 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 158.45, 132.97, 116.36, 114.43, 90.33, 83.45, 79.80, 63.57, 25.00, 14.97, 14.32.11B NMR (128 MHz, CDCl3) δ 32.77.HRMS (APCI) calcd for C18H25BO3

+ [(M+H)+]: 301.1970; found: 301.1970.

B O

O

4,4,5,5-tetramethyl-2-(4-(o-tolyl)but-3-yn-1-yl)-1,3,2-dioxaborolane (5b)Following general procedure A, 5a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (37mg, 68%).1H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 7.5 Hz, 1H), 7.15 (dd, J = 4.3, 0.9 Hz, 2H), 7.11 – 7.05 (m, 1H), 2.56 (t, J = 7.6 Hz, 2H), 2.41 (s, 3H), 1.26 (s, 12H), 1.17 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 140.16, 131.91, 129.40, 127.54, 125.53, 96.15, 83.51, 78.91, 25.0, 20.92, 14.48.11B NMR (128 MHz, CDCl3) δ 33.98.HRMS (APCI) calcd for C17H23BO2

+ [(M+H)+]: 271.1864; found: 271.1872.

B O

O

4,4,5,5-tetramethyl-2-(4-(p-tolyl)but-3-yn-1-yl)-1,3,2-dioxaborolane (6b).Following general procedure A, 6a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (43mg, 79%).1H NMR (400 MHz, CDCl3) δ 7.26 (t, J = 4.0 Hz, 2H), 7.15 – 6.95 (m, 2H), 2.50 (t, J

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= 7.6 Hz, 2H), 2.32 (s, 3H), 1.26 (s, 12H), 1.13 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 137.50, 131.57, 129.09, 121.31, 91.29, 83.51, 80.08, 29.92, 25.03, 21.60, 14.36.11B NMR (128 MHz, CDCl3) δ 33.95.HRMS (APCI) calcd for C17H23BO2

+ [(M+H)+]: 271.1864; found: 271.1853.

B O

O

2-(4-(3,5-dimethylphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7b).Following general procedure A, 7a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (47mg, 83%).1H NMR (400 MHz, CDCl3) δ 7.01 (s, 2H), 6.88 (s, 1H), 2.49 (t, J = 7.7 Hz, 2H), 2.26 (s, 6H), 1.26 (s, 12H), 1.13 (t, J = 7.7 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 137.81, 129.48, 129.41, 123.98, 91.37, 83.50, 80.27, 25.03, 21.30, 14.34.11B NMR (128 MHz, CDCl3) δ 33.82.HRMS (APCI) calcd for C18H25BO2

+ [(M+H)+]: 285.2020; found:285.2024.

B O

O

Cl

2-(4-(4-chlorophenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8b).Following general procedure A, 8a was used, (50mg, 86%). The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil.1H NMR (400 MHz, CDCl3) δ 7.29 (d, J = 8.5 Hz, 2H), 7.23 (d, J = 8.5 Hz, 2H), 2.50 (t, J = 7.6 Hz, 2H), 1.26 (s, 12H), 1.13 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 133.47, 132.93, 128.64, 122.90, 93.22, 83.56, 79.03, 25.02, 14.35.11B NMR (128 MHz, CDCl3) δ 34.03.HRMS (APCI) calcd for C16H20BClO2

+ [(M+H)+]: 291.1318; found:291.1322.

B O

O

Br

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2-(4-(4-bromophenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9b).Following general procedure A, 9a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil, (50mg, 75%).1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 8.6 Hz, 2H), 7.22 (d, J = 8.5 Hz, 2H), 2.49 (t, J = 7.6 Hz, 2H), 1.25 (s, 12H), 1.13 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 133.18, 131.56, 123.36, 121.64, 93.44, 83.56, 79.09, 25.01, 14.37.11B NMR (128 MHz, CDCl3) δ 33.56.HRMS (APCI) calcd for C16H20BBrO2

+ [(M+H)+]: 335.0812; found: 335.0812.

B O

O

F3CO

4,4,5,5-tetramethyl-2-(4-(4-(trifluoromethoxy)phenyl)but-3-yn-1-yl)-1,3,2-dioxaborolane (10b).Following general procedure A, 10a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (40mg, 59%).1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.7 Hz, 2H), 7.11 (d, J = 8.2 Hz, 2H), 2.50 (t, J = 7.6 Hz, 2H), 1.26 (s, 12H), 1.13 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 148.42, 133.10, 123.25, 121.87, 120.92, 93.14, 83.56, 83.04, 78.75, 25.00, 14.31.11B NMR (128 MHz, CDCl3) δ 33.56.HRMS (APCI) calcd for C17H21BF3O3

+ [(M+H)+]: 341.1530; found: 341.1535.

B O

O

OO

2-(4-(benzo[d][1,3]dioxol-5-yl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11b).Following general procedure A, 11a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (37mg, 62%).1H NMR (400 MHz, CDCl3) δ 6.87 (dd, J = 8.0, 1.2 Hz, 1H), 6.81 (d, J = 1.1 Hz, 1H), 6.69 (d, J = 8.0 Hz, 1H), 5.92 (s, 2H), 2.46 (t, J = 7.6 Hz, 2H), 1.24 (s, 12H), 1.10 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 147.41, 147.30, 125.98, 117.72, 111.81, 108.46, 101.29, 90.31, 83.51, 79.78, 25.03, 14.30.11B NMR (128 MHz, CDCl3) δ 33.85.

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HRMS (APCI) calcd for C17H21BO4+ [(M+H)+]: 301.1606; found: 301.1605.

B O

O

S4,4,5,5-tetramethyl-2-(4-(thiophen-2-yl)but-3-yn-1-yl)-1,3,2-dioxaborolane (12b).Following general procedure A, 12a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil, (43mg, 82%).1H NMR (400 MHz, CDCl3) δ 7.14 (dd, J = 5.2, 0.8 Hz, 1H), 7.08 (d, J = 3.1 Hz, 1H), 6.99 – 6.79 (m, 1H), 2.52 (t, J = 7.6 Hz, 2H), 1.27 (d, J = 7.1 Hz, 12H), 1.13 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 130.96, 126.91, 125.95, 96.17, 83.58, 73.23, 25.03, 14.63.11B NMR (128 MHz, CDCl3) δ 33.59.HRMS (APCI) calcd for C14H20BO2S+ [(M+H)+]:263.1272; found: 263.1272.

B O

O

O2-(4-(furan-2-yl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (13b).Following general procedure A, 13a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as pale yellow oil, (30mg, 60%).1H NMR (400 MHz, CDCl3) δ 7.31 (s, 1H), 6.43 (d, J = 3.5 Hz, 1H), 6.33 (d, J = 1.9 Hz, 1H), 2.53 (t, J = 7.7 Hz, 2H), 1.26 (s, 12H), 1.13 (t, J = 7.9 Hz, 2H).11B NMR (128 MHz, CDCl3) δ 33.94.13C NMR (101 MHz, CDCl3) δ 142.78, 137.95, 113.69, 110.78, 96.40, 83.34, 83.06, 70.46, 32.07, 25.00, 14.42. 11B NMR (128 MHz, CDCl3) δ 33.94.HRMS (APCI) calcd for C14H20BO3

+ [(M+H)+]: 247.1500; found:247.1503.

Experimental Procedures for Examples Described in Table 3.General Procedure B. In air, CuI 10 mol%, t-BuOLi 3 equiv, PPh3 20 mol%, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (1.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 10 min. Then diborylmethane (1) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And propargyl phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.

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B O

O

4,4,5,5-tetramethyl-2-(pent-3-yn-1-yl)-1,3,2-dioxaborolane (16b).Following general procedure B, 16a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (23mg, 58%).1H NMR (400 MHz, CDCl3) δ 2.27 – 2.15 (m, 2H), 1.75 (t, J = 2.5 Hz, 3H), 1.25 (s, 12H), 1.01 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 83.40, 81.06, 74.95, 24.98, 13.61, 3.70.11B NMR (128 MHz, CDCl3) δ 33.85.HRMS (APCI) calcd for C11H20BO2

+ [(M+H)+]: 195.1551; found:195.1553.

B O

O

2-(hex-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17b).Following general procedure B, 17a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (25mg, 60%).1H NMR (400 MHz, CDCl3) δ 2.24-2.15 (m, 2H), 2.15-2.10 (m, 2H), 1.25 (s, 12H), 1.09 (t, J = 7.5 Hz, 3H), 1.01 (t, J = 7.6 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 83.39, 81.23, 81.13, 29.92, 24.99, 14.53, 13.63, 12.6.11B NMR (128 MHz, CDCl3) δ 33.85.HRMS (APCI) calcd for C12H22BO2

+ [(M+H)+]: 209.1707; found: 209.1706.

B O

O

4,4,5,5-tetramethyl-2-(non-3-yn-1-yl)-1,3,2-dioxaborolane (18b).Following general procedure B, 18a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (25mg, 50%).1H NMR (400 MHz, CDCl3) δ 2.30 – 2.20 (m, 2H), 2.16 – 2.07 (m, 2H), 1.53 – 1.41 (m, 2H), 1.38 – 1.30 (m, 4H), 1.25 (s, 12H), 1.01 (t, J = 7.6 Hz, 2H), 0.88 (t, J = 7.0 Hz, 3H).13C NMR (101 MHz, CDCl3) δ 83.37, 81.86, 79.77, 31.28, 29.05, 24.99, 22.46, 18.96, 14.21, 13.66.11B NMR (128 MHz, CDCl3) δ 33.73.HRMS (APCI) calcd for C15H28BO2

+ [(M+H)+]: 251.2117; found: 251.2117.

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B O

O

Si

trimethyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-1-yn-1-yl)silane (19b).Following general procedure B, 19a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (27mg, 54%).1H NMR (400 MHz, CDCl3) δ 2.29 (t, J = 7.5 Hz, 2H), 1.22 (s, 12H), 1.01 (t, J = 7.5 Hz, 2H), 0.10 (s, 9H).13C NMR (101 MHz, CDCl3) δ 109.33, 83.54, 83.48, 25.00, 14.75, 0.36.11B NMR (128 MHz, CDCl3) δ 33.77.HRMS (APCI) calcd for C13H26BO2Si+ [(M+H)+]: 253.1790; found: 253.1804.

B O

O

OSi

tert-butyldimethyl((5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-yn-1-yl)oxy)silane (20b).Following general procedure B, 20a was used. The product was isolated by flash chromatography (2% ethyl acetate/hexane) as colorless oil, (43mg, 66%).1H NMR (400 MHz, CDCl3) δ 4.28 (t, J = 2.1 Hz, 2H), 2.29 (d, J = 8.0 Hz, 2H), 1.24 (s, 12H), 1.04 (t, J = 7.8 Hz, 2H), 0.90 (s, 9H), 0.10 (s, 6H).13C NMR (101MHz, CDCl3) δ 87.16, 83.48, 78.09, 52.24, 26.10, 25.01, 18.54, 13.68, 1.24, 0.21, -4.87.11B NMR (128 MHz, CDCl3) δ 33.92.HRMS (APCI) calcd forC17H34BO3Si+ [(M+H)+]: 325.2365; found: 325.2368.

Experimental Procedures for Examples Described in Table 4In air, Cu-catalyst, base, ligand, were added to a Schlenk tube equipped with a stir bar.

The vessel was evacuated and filled with argon (three cycles). Solvent (1.0 mL) was

added in turn by syringe under argon atmosphere at room temperature, and then

stirred at 60 oC for 10 min. Then diborylmethane was added in turn under an argon

atmosphere and stirred at 60 oC for 10 min. And cinnamyl electrophiles (X =

OPO(OEt)2, OBoc or Cl, 0.2mmol) were added in turn under an argon atmosphere.

The reaction mixture was stirred at 60 oC for 24 h, then diluted with EtOAc, filtered

through silica gel with copious washings (Et2O or EtOAc), and triphenylmethane

Page S12


(36.6 mg, 0.15 mmol) was added as internal standard. The product yield was

determined by GC.

Experimental Procedures for Examples Described in Table 5General Procedure C. In air, CuI 10 mol%, t-BuOLi 6 equiv, PPh3 20 mol%, were

added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled

with argon (three cycles). THF (1.0 mL) was added in turn by syringe under argon

atmosphere at room temperature, and then stirred at 60 oC for 10 min. Then

diborylmethane (1) was added in turn under an argon atmosphere and stirred at 60 oC

for 10 min. And propargyl chlorides (0.2 mmol) were added in turn under an argon

atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture

was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O

or EtOAc), concentrated and purified by column chromatography.

B O

O

O

2-(4-(4-methoxyphenyl)-2-methylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1d).Following general procedure C, 1c was used. The product was isolated by flash chromatography (1% ethyl acetate/hexane) as colorless oil, (38mg, 63%).1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.8 Hz, 2H), 6.79 (d, J = 8.8 Hz, 2H), 3.79 (s, 3H), 2.89 (dd, J = 14.4, 7.2 Hz, 1H), 1.28 (d, J = 2.6 Hz, 3H), 1.25 (s, 12H), 1.17 -1.14 (m, 2H).13C NMR (101MHz, CDCl3) δ 159.98, 152.75, 133.53, 114.56, 114.03, 85.91, 85.18, 82.76, 64.08, 55.45, 53.64, 27.96, 21.85.11B NMR (128 MHz, CDCl3) δ 33.85.HRMS (APCI) calcd forC17H24BO2+ [(M+H)+]: 301.1970; found: 301.1970.

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Me

Me

O

O

(Z)-(3-ethylidenehepta-1,4,5-triene-2,4-diyl)dibenzene (1f).Following general procedure C, 1c was used, CH3CN as solvent. The product was isolated by flash chromatography (1% ethyl acetate/hexane) as colorless oil, (47mg, 70%).1H NMR (400 MHz, CDCl3) δ 7.38 – 7.22 (m, 4H), 6.86 (t, J = 8.9 Hz, 4H), 5.79 (dd, J = 7.0 Hz, 1H), 5.48 (dd, J = 14.3, 7.1 Hz, 1H), 5.25 (s, 1H), 5.00 (s, 1H), 3.81 (d, J = 12.3 Hz, 6H), 1.78 (d, J = 7.1 Hz, 3H), 1.73 (d, J = 6.8 Hz, 3H).13C NMR (101 MHz, CDCl3) δ 204.50, 158.80, 158.41, 148.69, 138.36, 134.22, 129.99, 129.46, 128.62, 127.44, 114.81, 113.84, 102.90, 87.62, 55.28, 15.53, 13.85.HRMS (APCI) calcd for C23H25O2

+ [(M+H)+]: 333.1849; found: 333.1848.

B O

O

4,4,5,5-tetramethyl-2-(2-methyl-4-phenylbut-3-yn-1-yl)-1,3,2-dioxaborolane (2d).Following general procedure C, 2c was used. The product was isolated by flash chromatography (1% ethyl acetate/hexane) as colorless oil, (40mg, 74%). 1H NMR (400 MHz, CDCl3) δ 7.43 – 7.33 (m, 2H), 7.25-7.23 (m, 3H), 2.94 – 2.80 (m, 1H), 1.29 (d, J = 6.9 Hz, 3H), 1.26 (s, 12H), 1.12 -1.05 (m, 2H).13C NMR (101 MHz, CDCl3) δ 131.72, 128.29, 127.52, 124.40, 96.22, 83.43, 79.95, 25.03, 23.68, 22.69.11B NMR (128 MHz, CDCl3) δ 33.44HRMS (APCI) calcd for C17H24BO2

+ [(M+H)+]: 271.1864; found: 271.1848.

B O

O

F3CO

4,4,5,5-tetramethyl-2-(2-methyl-4-(4-(trifluoromethoxy)phenyl)but-3-yn-1-yl)-

1,3,2-dioxaborolane (3d).Following general procedure C, 3c was used. The product was isolated by flash

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chromatography (1% ethyl acetate/hexane) as colorless oil, (33mg, 47%).1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.4 Hz, 2H), 7.10 (d, J = 8.5 Hz, 2H), 2.89 (dd, J = 14.1, 6.9 Hz, 1H), 1.28 (d, J = 7.0 Hz, 3H), 1.25 (s, 12H), 1.14-1.05 (m, 2H).11B NMR (128 MHz, CDCl3) δ 32.77.13C NMR (101 MHz, CDCl3) δ 133.12, 123.25, 120.90, 83.47, 29.54, 25.03, 23.55, 22.65.HRMS (APCI) calcd for C18H23BF3O3

+ [(M+H)+]: 355.1687; found: 355.1705.

B O

O

Br

2-(4-(4-bromophenyl)-2-methylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-

dioxaborolane (4d).Following general procedure C, 4c was used. The product was isolated by flash chromatography (1% ethyl acetate/hexane) as colorless oil, (38mg, 55%).1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.3 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 2.88 (dd, J = 14.3, 7.1 Hz, 1H), 1.28 (d, J = 6.9 Hz, 3H), 1.25 (s, 12H), 1.17-1.05 (m, 2H)13C NMR (101 MHz, CDCl3) δ 133.20, 131.52, 128.76, 121.59, 97.49, 83.46, 78.99, 25.06, 24.99, 23.52, 22.72.11B NMR (128 MHz, CDCl3) δ34.03.HRMS (APCI) calcd for C17H23BBrO2

+ [(M+H)+]: 349.0969; found: 349.0975.

B O

O

2-(2-ethyl-4-phenylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5d).Following general procedure C, 5c was used. The product was isolated by flash chromatography (1% ethyl acetate/hexane) as colorless oil, (33mg, 58%).13C NMR (101 MHz, CDCl3) δ 131.53, 128.07, 127.27, 124.31, 94.69, 83.21, 80.96, 30.52, 29.63, 24.91, 24.73, 11.93.11B NMR (128 MHz, CDCl3) δ 34.01.HRMS (APCI) calcd for C18H26BO2

+ [(M+H)+]: 285.2020; found: 285.2020.

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B O

O

4,4,5,5-tetramethyl-2-(2-(phenylethynyl)pentyl)-1,3,2-dioxaborolane (6d).Following general procedure C, 6c was used, (32mg, 54%). The product was isolated by flash chromatography (1% ethyl acetate/hexane) as colorless oil.1H NMR (400 MHz, CDCl3) δ 7.39 – 7.33 (m, 2H), 7.24 (d, J = 1.7 Hz, 3H), 2.85 – 2.69 (m, 1H), 1.57 – 1.40 (m, 4H), 1.26 (s, 12H), 1.11 (dd, J = 9.4, 7.7 Hz, 2H), 0.94 (t, J = 7.1 Hz, 3H).13C NMR (101 MHz, CDCl3) δ 131.73, 128.28, 127.47, 124.52, 95.10, 83.43, 81.01, 40.03, 27.95, 25.11, 24.95, 20.90, 14.19.11B NMR (128 MHz, CDCl3) δ 33.94.HRMS (APCI) calcd for C19H28BO2

+ [(M+H)+]: 299.2177; found: 299.2177.

B O

O

2-(2-isopropyl-4-phenylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

(7d).Following general procedure C, 7c was used. The product was isolated by flash chromatography (1% ethyl acetate/hexane) as colorless oil, (30mg, 50%).1H NMR (400 MHz, CDCl3) δ 7.45 – 7.34 (m, 2H), 7.29 – 7.11 (m, 3H), 2.70 (dt, J = 10.5, 5.4 Hz, 1H), 1.73 (td, J = 13.3, 6.7 Hz, 1H), 1.26 (s, 12H), 1.12 (d, J = 10.4 Hz, 2H), 1.02 (t, J = 6.7 Hz, 6H).13C NMR (101 MHz, CDCl3) δ131.73, 128.28, 127.44, 124.61, 93.50, 83.44, 82.12, 35.03, 33.80, 25.19, 24.86, 21.18, 18.66.11B NMR (128 MHz, CDCl3) δ 34.37.HRMS (APCI) calcd for C19H28BO2

+ [(M+H)+]: 299.2177; found: 299.2177.

Experimental Procedures for Examples Described in Scheme2.General Procedure D. In air, CuI 10 mol%, t-BuOLi 3 equiv, PPh3 20 mol%, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (1.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 10 min. Then deuterated gem-diborylalkanes was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And propargyl phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.

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B O

O

D

D

4,4,5,5-tetramethyl-2-(4-phenylbut-3-yn-1-yl-1,1-d2)-1,3,2-dioxaborolane (2e).Following general procedure D, 1a and di-deuterated gem-diborylalkanes was used. The product was isolated by flash chromatography (1% ethyl acetate /hexane) as colorless oil, (45mg, 87%).1H NMR (400 MHz, CDCl3) δ 7.47 – 7.35 (m, 2H), 7.28 – 7.20 (m, 3H), 2.51 (s, 2H), 1.27 (s, 12H).13C NMR (101 MHz, CDCl3) δ 131.70, 128.33, 127.56, 124.39, 92.12, 83.52, 80.06, 25.03, 14.20.11B NMR (128 MHz, CDCl3) δ 33.90.HRMS (APCI) calcd for C16H20D2BO2

+ [(M+H)+]: 259.1883; found: 259.1836.

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IV. References

[1] K. Semba, N. Bessho, T. Fujihara, J. Terao, Y. Tsuji, Angew. Chem. Int. Ed. 2014,

53, 9007.

[2] Z.-Q. Zhang, C.-T. Yang, L.-J. Liang, B. Xiao, X. Lu, J.-H. Liu, Y.-Y. Sun,

T. B. Marder, Y. Fu, Org. Lett. 2014, 16, 6342.

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Ⅴ. NMR Spectra and Analysis1H NMR of bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methane-d2 (2)

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1H NMR, 13C NMR and 11B NMR of 2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl furan-2-carboxylate (1b)

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1H NMR, 13C NMR and 11B NMR of 2-(4-(4-methoxyphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(4-methoxyphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(3b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(4-ethoxyphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(4b)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(4-(o-tolyl)but-3-yn-1-yl)-1,3,2-dioxaborolane(5b)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(4-(p-tolyl)but-3-yn-1-yl)-1,3,2-dioxaborolane(6b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(3,5-dimethylphenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(7b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(4-chlorophenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(8b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(4-bromophenyl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(9b)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(4-(4-(trifluoromethoxy)phenyl)but-3-yn-1-yl)-1,3,2-dioxaborolane(10b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(benzo[d][1,3]dioxol-5-yl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(11b)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(4-(thiophen-2-yl)but-3-yn-1-yl)-1,3,2-dioxaborolane(12b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(furan-2-yl)but-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(13b)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(pent-3-yn-1-yl)-1,3,2-dioxaborolane(16b)

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1H NMR, 13C NMR and 11B NMR of2-(hex-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(17b)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(non-3-yn-1-yl)-1,3,2-dioxaborolane(18b)

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1H NMR, 13C NMR and 11B NMR oftrimethyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-1-yn-1-yl)silane(19b)

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1H NMR, 13C NMR and 11B NMR oftert-butyldimethyl((5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-yn-1-yl)oxy)silane(20b)

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1H NMR, 13C NMR and 11B NMR of2-(4-(4-methoxyphenyl)-2-methylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(1d)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(2-methyl-4-phenylbut-3-yn-1-yl)-1,3,2-dioxaborolane(2d)

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1H NMR and 13C NMR of (Z)-(3-ethylidenehepta-1,4,5-triene-2,4-diyl)dibenzene (1f).

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(2-methyl-4-(4-(trifluoromethoxy)phenyl)but-3-yn-1-yl)-1,3,2-dioxaborolane(3d)

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1H NMR, 13C NMR and 11B NMR of2-(4-(4-bromophenyl)-2-methylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(4d)

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13C NMR and 11B NMR of2-(2-ethyl-4-phenylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(5d)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(2-(phenylethynyl)pentyl)-1,3,2-dioxaborolane(6d)

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1H NMR, 13C NMR and 11B NMR of2-(2-isopropyl-4-phenylbut-3-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(7d)

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1H NMR, 13C NMR and 11B NMR of4,4,5,5-tetramethyl-2-(4-phenylbut-3-yn-1-yl-1,1-d2)-1,3,2-dioxaborolane(1e)

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copper-catalyzed propargylation of diborylmethane · copper-catalyzed propargylation of...

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