Benzaldehyde → alpha-(Nitromethyl)benzenemethanol

HRID 505008Notes

Reaction equation

NC(N)=N.[CH:5](=[O:12])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C(N)CC1C=CC=CC=1.[N+:22]([CH3:25])([O-:24])=[O:23]>>[N+:22]([CH2:25][CH:5]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[OH:12])([O-:24])=[O:23]

Participants

Reactant 4

HCID 240Benzaldehyde

HCID 1001Phenethylamine

HCID 3520Guanidine4×

HCID 6375Nitromethane

Product 1

HCID 226830alpha-(Nitromethyl)benzenemethanolYield 31%

Procedure

In recent years, attention has been paid to optically active guanidine compounds as base catalysts for asymmetric nucleophilic-type reactions, a representative of which is an asymmetric aldol-type reaction. However, all of the previously known optically active guanidine compounds have central chirality as a chiral element, and it cannot be said that molecular design based on only such the central chirality is sufficient to draw the potential usefulness of such optically active guanidine compounds. As one of the reactions using an optically active guanidine compound which is constructed based on central chirality as an asymmetric base catalyst, a nitroaldol reaction is reported (Non-Patent Literature 1: Tetrahedron: Asymmetry, 1994, 5, 1393; Non-Patent Literature 2: Tetrahedron Lett., 2003, 44, 8677). The Non-Patent Literature 1 disclosed that in the aldol condensation between benzaldehyde and nitromethane, optically active guanidines having a phenethylamine skeleton as an optically active site are used as an asymmetric catalyst, and 2-nitro-1-phenylethanol is obtained in a yield of 31% and an asymmetric yield of 33% ee.

Workup

customan asymmetric aldol-type reaction
customa nitroaldol reaction

Sources & evidence

ORD record: ord-e2ca5936b391455cb1b94310decd6b0a
Source dataset: uspto-grants-2010_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07781425B2

Reaction notes

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