1,3-Oxazolidine → Benzaldehyde

HRID 2358466Notes

Reaction equation

HRID 2358466 reaction equation
[CH2:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C@@H:3](N)[C@H:2]1O.[O:12]1CCNC1>>[CH:1](=[O:12])[C:9]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1.[C:4]1([C:3]#[CH:2])[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

4

Reactant 2

HCID 5366831,3-OxazolidineHCID 2725045(1R,2S)-(+)-cis-1-Amino-2-indanol

Product 2

HCID 240BenzaldehydeHCID 10821Phenylacetylene

Procedure

Although mono-oxazolidines have been used for alkylation and alkynylation of aldehydes, the C2-symmetry of bisoxazolidine 1 provides superior results and appears to be crucial for both catalytic activity and asymmetric induction. For example, see: (a) Prasad, K. R. K.; Joshi, N. N. J. Org. Chem. 1997, 62, 3770-3771; (b) Kang, Y.; Wang, R.; Liu, L.; Da, C.; Yan, W.; Xu, Z. Tetrahedron Lett. 2005, 46, 863-865; and (c) Kang, Y. F.; Liu, L.; Wang, R.; Zhou, Y.-F. Yan, W. J. Adv. Synth. Catal. 2005, 347, 243-247. For comparison, we prepared a (1R,2S)-cis-1-amino-2-indanol-derived oxazolidine 2 using cyclohexanone instead of cyclohexanedione and tested its catalytic performance under the same reaction conditions. Alkynylation of benzaldehyde with phenylacetylene in the presence of 10 mol % of 2 gave the corresponding alcohol in only 76% yield and 17% ee (FIG. 3B).

Workup

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Sources & evidence

ORD record
ord-5da467f832f3477aae195befedbc52c4
Source dataset
uspto-grants-2010_07
Patent number
US07763734B2

Reaction notes

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