5-Oxo-5,6,7,8-tetrahydronaphthalene-1-carbonitrile → (R)-5-hydroxy-5,6,7,8-tetrahydronaphthalene-1-carbonitrile

HRID 1053733Notes

Reaction equation

[O:1]=[C:2]1[CH2:11][CH2:10][CH2:9][C:8]2[C:7]([C:12]#[N:13])=[CH:6][CH:5]=[CH:4][C:3]1=2>CC1C=CC(C(C)C)=CC=1.CC1C=CC(S([N-][C@@H]([C@H](N)C2C=CC=CC=2)C2C=CC=CC=2)(=O)=O)=CC=1.Cl[Ru+].CCN(CC)CC>[OH:1][C@@H:2]1[CH2:11][CH2:10][CH2:9][C:8]2[C:7]([C:12]#[N:13])=[CH:6][CH:5]=[CH:4][C:3]1=2

Participants

Conditions

Temperature: 30 °C

Procedure

To a stirred solution of 5-oxo-5,6,7,8-tetrahydronaphthalene-1-carbonitrile INT-1 (3.0 g, 17.5 mmol) in 5:1 HCO2:NEt3 (24 mL) was added RuCl(p-cymene)[(R,R)-Ts-DPEN] (0.13 g, 0.26 mmol). The mixture was stirred at 30° C. for 15 h then partitioned between EA and H2O. The combined organic layers were dried over Na2SO4 and chromatographed (EA/hex) to provide 2.99 g (99%) of (R)-5-hydroxy-5,6,7,8-tetrahydronaphthalene-1-carbonitrile INT-2 as a white solid. LCMS-ESI (m/z) calculated for C11H11NO: 173.2; found 174.1 [M+H]+, 156.1 [M−NH4]+, tR=2.60 min. 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J=7.8 Hz, 1H), 7.54 (dt, J=8.7, 4.4 Hz, 1H), 7.34-7.26 (m, 1H), 4.85-4.71 (m, 2H), 3.48 (s, 1H), 3.13-2.96 (m, 1H), 2.90 (ddd, J=17.7, 7.8, 5.6 Hz, 1H), 2.15-1.95 (m, 2H), 1.97-1.76 (m, 2H). Chiral HPLC: (R)-5-hydroxy-5,6,7,8-tetrahydronaphthalene-1-carbonitrile was eluted with 5% IPA/hexane: 99.1% ee, tR=15.3 min.

Workup

customthen partitioned between EA and H2O
dry with materialThe combined organic layers were dried over Na2SO4
customchromatographed (EA/hex)

Sources & evidence

ORD record: ord-dbe3c5c2ed6b460b98a96c99c28b0a71
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09394264B2

Reaction notes

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