HCID 11480063, compound → HCID 86602888, compound

HRID 2252483Notes

Reaction equation

HRID 2252483 reaction equation
[Si:1]([O:8][C@@H:9]([CH2:35][C:36](=[O:64])[C:37]#[C:38][C@H:39]([CH3:63])[C@H:40]([O:55][Si:56]([C:59]([CH3:62])([CH3:61])[CH3:60])([CH3:58])[CH3:57])[C@@H:41]([CH3:54])[CH2:42][C@@H:43]([CH3:53])[CH2:44][O:45][Si:46]([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:48])[CH3:47])[C@H:10]([CH3:34])/[CH:11]=[CH:12]/[CH2:13][O:14][C:15]([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]>CC(O)C>[Si:1]([O:8][C@@H:9]([CH2:35][C@H:36]([OH:64])[C:37]#[C:38][C@H:39]([CH3:63])[C@H:40]([O:55][Si:56]([C:59]([CH3:60])([CH3:61])[CH3:62])([CH3:58])[CH3:57])[C@@H:41]([CH3:54])[CH2:42][C@@H:43]([CH3:53])[CH2:44][O:45][Si:46]([C:49]([CH3:50])([CH3:51])[CH3:52])([CH3:48])[CH3:47])[C@H:10]([CH3:34])/[CH:11]=[CH:12]/[CH2:13][O:14][C:15]([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)([C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

3

Reactant 1

HCID 11480063HCID 11480063, compound

Product 1

HCID 86602888HCID 86602888, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

Ynone 32 (5.28 g, 5.71 mmol) was taken up in i-PrOH (58 mL). The (S,S)-Noyori catalyst (0.77 g, 1.15 mmol, 20 mol %) was added in one portion and the solution was stirred overnight. The solvent was removed under vacuum, and the crude residue was purified by flash chromatography on silica gel (hexane/EtOAc 97:3), affording propargylic alcohol 33 (4.18 g, 79%) as a pale yellow oil: IR (CHCl3) 3469, 2955, 2856, 1471, 1448, 1252, 1084, 836, 774 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.55 (m, 6H), 7.36 (m, 9H), 5.71 (m, 2H), 4.59 (m, 1H), 4.03 (quint, J=3.9 Hz, 1H), 3.65 (d, J=3.9 Hz, 2H), 3.58 (dd, J=4.6, 3.2 Hz, 1H), 3.55 (dd, J=10.1, 5.1 Hz, 1H), 3.38 (dd, J=9.7, 6.8 Hz, 1H), 2.71 (m, 1H), 2.50 (m, 1H), 2.32 (d, J=5.4 Hz, 1H), 1.88 (m, 1H), 1.80 (m, 2H), 1.55 (m, 1H), 1.23 (d, J=7.1 Hz, 3H), 1.11 (d, J=6.8 Hz, 3H), 0.98 (m, 34H), 0.20 (s, 3H), 0.17 (s, 3H), 0.16 (s, 3H), 0.14 (s, 3H), 0.12 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 144.3, 134.0, 128.6, 127.8, 127.1, 126.9, 88.1, 86.8, 83.0, 72.6, 68.3, 65.8, 65.1, 59.5, 41.9, 40.3, 38.7, 33.5, 33.2, 32.1, 26.0, 25.9, 18.4, 18.1, 17.7, 17.4, 15.7, 15.3, 14.2, −3.9, −4.0, −4.4, −4.5, −5.3; LRMS (ESI) 949.7 [M+Na]+, 413.3, 243.1; HRMS (ESI) calcd for C56H90O5Si3Na 949.5994 [M+Na]+, found 949.6018; [α]20D−10.0 (c 1.2, CHCl3).

Workup

  1. customThe solvent was removed under vacuum
  2. customthe crude residue was purified by flash chromatography on silica gel (hexane/EtOAc 97:3)

Sources & evidence

ORD record
ord-5813e468d0fa4f718d42584b9add2eac
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

Loading…