Triphenylphosphine → (1S,3'R,4'S,5'S,6'R)-6'-(aminomethyl)-5-chloro-6-(4-ethylbenzyl)-3',4',5',6'-tetrahydro-3H-spiro[isobenzofuran-1,2'-pyran]-3',4',5'-triol

HRID 1716964Notes

Reaction equation

HRID 1716964 reaction equation
[N:1]([CH2:4][C@H:5]1[O:10][C@@:9]2([C:18]3[C:13](=[CH:14][C:15]([Cl:28])=[C:16]([CH2:19][C:20]4[CH:25]=[CH:24][C:23]([CH2:26][CH3:27])=[CH:22][CH:21]=4)[CH:17]=3)[CH2:12][O:11]2)[C@H:8]([OH:29])[C@@H:7]([OH:30])[C@@H:6]1[OH:31])=[N+]=[N-].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>C1COCC1.O>[NH2:1][CH2:4][C@H:5]1[O:10][C@@:9]2([C:18]3[C:13](=[CH:14][C:15]([Cl:28])=[C:16]([CH2:19][C:20]4[CH:21]=[CH:22][C:23]([CH2:26][CH3:27])=[CH:24][CH:25]=4)[CH:17]=3)[CH2:12][O:11]2)[C@H:8]([OH:29])[C@@H:7]([OH:30])[C@@H:6]1[OH:31]

Participants

4

Reactant 2

HCID 11776TriphenylphosphineHCID 59013455(1S,3'R,4'S,5'S,6'R)-6'-(azidomethyl)-5-chloro-6-(4-ethylbenzyl)-3',4',5',6'-tetrahydro-3H-spiro[isobenzofuran-1,2'-pyran]-3',4',5'-triol

Product 1

HCID 59013483(1S,3'R,4'S,5'S,6'R)-6'-(aminomethyl)-5-chloro-6-(4-ethylbenzyl)-3',4',5',6'-tetrahydro-3H-spiro[isobenzofuran-1,2'-pyran]-3',4',5'-triolYield 59.5%

Reagents, catalysts & solvents 1

HCID 21881883Oxolane--water (1/1)Solvent

Procedure

To a solution of (1S,3′R,4′S,5′S,6′R)-6′-(azidomethyl)-5-chloro-6-(4-ethylbenzyl)-3′,4′,5′,6′-tetrahydro-3H-spiro[isobenzofuran-1,2′-pyran]-3′,4′,5′-triol (25 mg, 0.056 mmol) in 0.5 mL of THF/H2O (4:1), was added PPh3 (43 mg, 0.164 mmol). The solution was stirred at room temperature for 4.5 h. Then the volatiles were removed under reduced pressure using a rotary evaporator. The resulting residue was purified by preparative HPLC to give 14 mg of title compound. 1H NMR (CD3OD, 300 MHz) δ 7.39 (s, 1H), 7.23 (s, 1H), 7.10 (s, 4H), 5.16 (d, J=12.8 Hz, 1H), 5.10 (d, J=12.8 Hz, 1H), 4.13 (d, J=15.6 Hz, 1H), 4.05 (d, J=15.6 Hz, 1H), 4.02-3.94 (m, 1H), 3.75 (dd, J=4.1, 1.1 Hz, 2H), 3.34-3.32 (m, 2H□, 2.98-2.91 (m, 1H □, 2.60 (q, J=7.5 Hz, 2H), 1.20 (t, J=7.5 Hz, 3H); MS ESI (m/z) 420 (M+1)+, calc. 419.

Workup

  1. customThen the volatiles were removed under reduced pressure
  2. customa rotary evaporator
  3. customThe resulting residue was purified by preparative HPLC

Sources & evidence

ORD record
ord-7c8a8251ed274f97bd81f12bc1468afe
Source dataset
uspto-grants-2010_09
Patent number
US07803778B2

Reaction notes

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