HCID 12279339, compound → HCID 15605927, compound

HRID 1886854Notes

Reaction equation

HRID 1886854 reaction equation
Cl[C:2]1[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=1[CH2:4][CH2:5][CH:6]=[O:7].[O:12]=[C:13]([C:20]1[CH:25]=[CH:24][C:23]([Br:26])=[CH:22][CH:21]=1)/[CH:14]=[CH:15]/[C:16]([O:18][CH3:19])=[O:17]>C(Cl)(Cl)Cl>[CH2:4]([C@H:5]1[C@@H:15]([C:16]([O:18][CH3:19])=[O:17])[CH:14]=[C:13]([C:20]2[CH:21]=[CH:22][C:23]([Br:26])=[CH:24][CH:25]=2)[O:12][C:6]1=[O:7])[C:3]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:2]=1

Participants

4

Reactant 2

HCID 12279339HCID 12279339, compoundHCID 218597263-(2-Chlorophenyl)propanal

Product 1

HCID 15605927HCID 15605927, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Prepared according to the general procedure from 2-chloro-hydrocinnamaldehyde and (E)-methyl 4-oxo-4-(4-bromophenyl)but-2-enoate using 0.5 mol % 1 as the catalyst in 80% yield as a 6:1 mixture of diastereomers (white solid). [α]D20 (c 1.23, CHCl3)=+112.1; mp=139-141° C.; 1H NMR (400 MHz, CDCl3) δ 7.53-7.47 (m, 4H), 7.35-7.25 (m, 5H), 7.19-7.17 (m, 2H), 5.81 (d, 1H, J=7.1 Hz), 5.74* (d, 1H, J=5.6 Hz), 4.23 (q, 2H, J=7.0 Hz), 4.13* (q, 2H, J=7.2 Hz), 3.55 (dd, 1H, J=14.4, 4.7 Hz), 3.40-3.35* (m, 1H), 3.27-3.24* (m. 1H), 3.25 (dd, 1H, J=7.1, 5.8 Hz), 3.14* (dd, 1H, J=13.8, 5.7 Hz), 3.03-2.97 (m, 1H), 2.91* (dd, 1H, J=13.8, 8.8 Hz), 2.77 (dd, 1H, J=14.3, 10.0 Hz), 1.30 (t, 3H, J=7.0 Hz), 1.24* (t, 3H, J=7.2 Hz); 13C NMR (100 MHz, CDCl3) δ 170.2, 168.7, 151.7, 138.1, 131.9, 130.9, 1294, 129.2, 129.0, 127.4, 127.1, 126.5, 124.0, 98.7, 96.7, 66.1, 62.1, 61.9, 42.8, 42.2, 41.5, 40.7, 35.5, 33.3, 15.5, 14.3, 14.2; IR (thin film) ν 3087, 3027, 2980, 1778, 1731, 1489, 1455, 1176, 1069, 1009 cm−1; HRMS (ESI) calcd for C21H19BrO4 [M+Na]+ 437.0358, found 437.0359; 99% ee (3S,4S)-isomer as determined by HPLC (AD-H, 9:1 hexanes/i-PrOH), tr (3S,4S)=57.6 min, tr (3R,4R)=25.4 min.

Workup

  1. customPrepared

Sources & evidence

ORD record
ord-71a1076dfdcb4d71ae49ac6b2021ac93
Source dataset
uspto-grants-2013_08
Patent number
US08501658B2

Reaction notes

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