4,4,5,5-Tetramethyl[1,3,2]dioxaborolane → HCID 117974371, compound

HRID 1776087Notes

Reaction equation

HRID 1776087 reaction equation
CC1(C)C(C)(C)OBO1.[CH3:10][CH:11]([CH3:17])[CH2:12]/[CH:13]=[CH:14]/[CH:15]=[CH2:16].[CH3:18][O:19][C:20]1[CH:31]=[CH:30][C:23]([CH2:24][O:25][C@@H:26]([CH3:29])[CH:27]=[O:28])=[CH:22][CH:21]=1>C1(C)C=CC=CC=1.C1CC=CCCC=C1.C1CC=CCCC=C1.[Ni].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1>[CH3:18][O:19][C:20]1[CH:31]=[CH:30][C:23]([CH2:24][O:25][C@H:26]([C@H:27]([OH:28])[C@H:14]([CH:15]=[CH2:16])[CH2:13][CH2:12][CH:11]([CH3:17])[CH3:10])[CH3:29])=[CH:22][CH:21]=1

Participants

7

Reactant 3

HCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 10582757HCID 10582757, compoundHCID 11063298HCID 11063298, compound

Product 1

HCID 117974371HCID 117974371, compoundYield 69%

Reagents, catalysts & solvents 3

HCID 75806TricyclohexylphosphineCatalystHCID 6433264Bis(1,5-cyclooctadiene)nickelCatalystHCID 1140TolueneSolvent2×

Procedure

Under a strict nitrogen atmosphere an oven-dried round-bottomed flask with a magnetic stir bar was charged with bis(1,5-cyclooctadiene)nickel(0) (0.297 grams (g), 1.080 millimole (mmol)) and tricyclohexylphosphine (0.379 g, 1.35 mmol). Anhydrous toluene (40 milliliters (mL)) followed by 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.34 ml, 57.5 mmol) and (E)-6-methylhepta-1,3-diene (11.9 g, 54.0 mmol), prepared according to the procedure disclosed in Wang, Y.; West, F. G. Synthesis 2002, 99-103, were added to the flask and the reaction was allowed to stir at room temperature for 20 hours (h), as described in the diene hydroboration conditions reported in Ely, R. J.; Morken, J. P. J. Am. Chem. Soc. 2010, 132, 2534-2535. To the mixture was added a solution of (S)-2-((4-methoxybenzyl)oxy)propanal (10.49 g, 54.0 mmol) in anhydrous toluene (5 mL) at −20° C. The reaction mixture was slowly warmed to room temperature and stirred at room temperature for 40 h, then quenched with MeOH and stirred for an additional 2 h. The crude mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (SiO2; gradient, hexanes/ethyl acetate) to yield the title compound as a colorless oil (11.3 g, 69%): IR (neat) 3467, 2925, 2868, 1513, 1247 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.27-7.22 (m, 2H), 6.90-6.85 (m, 2H), 5.51-5.38 (m, 1H), 5.08-4.96 (m, 2H), 4.52-4.40 (m, 2H), 3.80 (s, 3H), 3.66 (ddd, J=9.2, 3.1, 2.1 Hz, 1H), 3.59-3.49 (m, 1H), 2.26-2.20 (m, 1H), 2.04-1.95 (m, 1H), 1.90-1.80 (m, 1H), 1.59-1.43 (m, 1H), 1.29-1.14 (m, 2H), 1.13 (d, J=6.2 Hz, 3H), 1.10-0.99 (m, 1H), 0.87 (d, J=6.4 Hz, 3H), 0.86 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 159.19, 138.56, 130.59, 129.22, 116.59, 113.82, 75.89, 74.46, 70.11, 55.29, 47.18, 36.05, 28.57, 28.23, 22.98, 22.42, 12.17; ESIMS m/z 329.2 ([M+Na]+).

Workup

  1. customprepared
  2. customSynthesis 2002, 99-103
  3. additionwere added to the flask
  4. temperatureThe reaction mixture was slowly warmed to room temperature
  5. stirringstirred at room temperature for 40 h
  6. customquenched with MeOH
  7. stirringstirred for an additional 2 h
  8. concentrationThe crude mixture was concentrated under reduced pressure
  9. custompurified by column chromatography on silica gel (SiO2; gradient, hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-99e0c12dd60d4ef99ee266c8b010509b
Source dataset
uspto-grants-2016_02
Patent number
US09265253B2

Reaction notes

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