m-Chloroperbenzoic acid → ((2'S,3'R,4'S,5'R,6'R)-3',4',5'-tris(benzyloxy)-6'-(benzyloxymethyl)-7-chloro-6-(4-ethylbenzyl)-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-2-yl)methanol

HRID 1713601Notes

Reaction equation

HRID 1713601 reaction equation
[CH2:1]([C@:4]1([C:43]2[CH:48]=[C:47]([CH2:49][C:50]3[CH:55]=[CH:54][C:53]([CH2:56][CH3:57])=[CH:52][CH:51]=3)[C:46]([Cl:58])=[CH:45][C:44]=2[OH:59])[C@H:9]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C@@H:8]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C@H:7]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@@H:6]([CH2:34][O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[O:5]1)[CH:2]=[CH2:3].ClC1C=C(C=CC=1)C(OO)=[O:65]>C(Cl)Cl>[CH2:11]([O:10][C@@H:9]1[C@@H:8]([O:18][CH2:19][C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[C@H:7]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@@H:6]([CH2:34][O:35][CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[O:5][C@:4]21[C:43]1[C:44](=[CH:45][C:46]([Cl:58])=[C:47]([CH2:49][C:50]3[CH:51]=[CH:52][C:53]([CH2:56][CH3:57])=[CH:54][CH:55]=3)[CH:48]=1)[O:59][CH:2]([CH2:3][OH:65])[CH2:1]2)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 687951322-((2S,3R,4S,5R,6R)-2-allyl-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)tetrahydro-2H-pyran-2-yl)-5-chloro-4-(4-ethylbenzyl)phenol

Product 1

HCID 68793779((2'S,3'R,4'S,5'R,6'R)-3',4',5'-tris(benzyloxy)-6'-(benzyloxymethyl)-7-chloro-6-(4-ethylbenzyl)-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-2-yl)methanolYield 24%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 34 (70 mg, 86 μmol) in anhydrous DCM (1 mL) was added 3-chlorobenzoperoxoic acid (23 mg, 104 μmol, 1.2 equiv). The reaction was stirred overnight, directly loaded onto a preparatory TLC plate, and eluted with 15% EtOAc in petroleum ether to give 39 (17 mg, 24% yield), a single diastereomer. 1H NMR (300 MHz, CDCl3) δ 7.14-7.32 (m, 18H), 6.98 (d, J=8.1 Hz, 2H), 6.96 (s, 1H), 6.90 (d, J=8.1 Hz, 2H), 6.79-6.83 (m, 2H), 4.85 (d, J=10.8 Hz, 1H), 4.80 (s, 2H), 4.58 (d, J=10.8 Hz, 1H), 4.57 (d, J=12.0 Hz, 1H), 4.45 (d, J=12.0 Hz, 1H), 4.37 (d, J=10.8 Hz, 1H), 4.07-4.15 (m, 1H), 4.05 (d, J=15.6 Hz, 1H), 3.61-3.91 (m, 10H), 2.49 (q, J=7.5 Hz), 2.08-2.35 (m, 3H), 1.12 (t, J=7.5 Hz, 3H). LCMS m/z 826 (M+H), 848 (M+Na).

Workup

  1. washeluted with 15% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-a4fb22004ef240bc9b98e2f93d47a41d
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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