Reaktion #364677

Reaktionsgleichung

(S)-methyl 1-(1,3-benzodioxol-5-yl)-3-[(fluorosulfonyl)oxy]-5-propoxy-1H-indene-2-carboxylate

[4-methoxy-2-(phenylmethoxy)phenyl]boronic acid

Compound ( u )

[4-methoxy-2-(phenylmethoxy)phenyl]boronic acid

K2CO3

Norit

charcoal

→

(S)-methyl-1-(1,3-benzodioxol-5-yl)-3-[4-methoxy-2-(phenylmethoxy)phenyl]-5-propoxy-1H-indene-2-carboxylate

Ausbeute 99.6%

Lösungsmittel

EtOH

toluene

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturheated to 70° C. for 45 min
2. 2
   TemperaturThe mixture was cooled to room temperature
3. 3
   Filtrationfiltered through celite (10 g)
4. 4
   EinengenThe filtrate was then concentrated in vacuo

Vorschrift

A 50 mL three-necked flask under nitrogen was charged with (S)-methyl 1-(1,3-benzodioxol-5-yl)-3-[(fluorosulfonyl)oxy]-5-propoxy-1H-indene-2-carboxylate (600 mg, 1.3 mmol), [4-methoxy-2-(phenylmethoxy)phenyl]boronic acid (Compound (u)) (330 mg, 1.4 mmol), toluene (16 mL), EtOH (2 mL), and Pd(dppf)Cl2 catalyst (4.8 mg, 0.005 mmol). The mixture was stirred for 0.5 h at room temperature followed by the addition of 1.3 M K2CO3 solution (2.0 mL, 2.6 mmol) and heated to 70° C. for 45 min. The mixture was cooled to room temperature, charged with Norit A charcoal (5 g) and filtered through celite (10 g). The filtrate was then concentrated in vacuo affording (S)-methyl-1-(1,3-benzodioxol-5-yl)-3-[4-methoxy-2-(phenylmethoxy)phenyl]-5-propoxy-1H-indene-2-carboxylate as a yellow gum (731 mg, 99% yield). (viii)a. (S)-Methyl 1-(1,3-benzodioxol-5-yl)-3-[4-methoxy-2-(phenylmethoxy)phenyl]-S-propoxy-1H-indene-2-carboxylate A 500 mL three-necked round-bottomed flask under nitrogen was charged with (S) -Methyl-1-(1,3-benzodioxol-5-y)-3-[(fluorosulfonyl)oxy]5-propoxy-1H-indene-2-carboxylate (10 g, 21.46 mmol), [4-methoxy-2-(phenylmethoxy)phenyl]boronic acid (Compound (u)) (5.53 g, 21.46 mmol), toluene (200 mL), EtOH (16 mL), and Pd(dppf)Cl2 catalyst (78.5 mg, 0.11 mmol). The mixture was stirred for 0.5 h at room temperature followed by the addition of K2CO3 solution (5.92 g in 16 mL H,O, 42.92 mmol) and heated to 70° C. for 45 min. The mixture was cooled to room temperature, washed with H2O (2×50 mL), brine (1×50 mL), dried over MgSO4 and the solvent removed in vacuo. The crude product was purified via recrystallization from 2-methoxy ethanol to afford (S)-Methyl 1-(1,3-benzodioxol-5-yl)-3-[4-methoxy-2-(phenylmethoxy)phenyl]-5-propoxy-1H-indene-2-carboxylate as a light yellow solid (8.7 g, 75% yield): mp 114.0-117.0° C. 1H NMR (DMSO, 335 K) δ7.3-7.2 (m, 8H), 7.1 (d, J=8.3 Hz, 1H), 6.9 (dd, J=2.4, 8.2 Hz, 1H), 6.85 (d, J=2.1 Hz, 1H), 6.75 (dd, J=2.3, 8.2 Hz, 1H), 6.65 (d, J=2.3 Hz, 1H), 6.55 ; (d, J=1.5 Hz, 1H), 5.9 (s, 2H), 5.1 (s, 2H), 4.9 (s, 1H), 3.9-3.8 (m, 5H), 3.4 (s, 3H), 1.65 (quintet, J=7.8 Hz, 2H), 0.9 (t, J=7.4 Hz, 3H)

Quelle