Reaction #2006450

ord-05c7a7d35dae46c982a00b13e58ad6f4

Reaction equation

CC(C)(C)OC(=O)N1CCC(=O)C1
N-Boc-3-pyrrolidinone
O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
D-glucose
NC(=O)c1ccc[n+]([C@@H]2O[C@H](COP(=O)(O)OP(=O)(O)OC[C@H]3O[C@@H](n4cnc5c(N)ncnc54)[C@H](O)[C@@H]3O)[C@@H](O)[C@H]2O)c1
NAD+
Cc1ncc(COP(=O)(O)O)c(C=O)c1O
pyridoxal phosphate
CC(C)(C)OC(=O)N1CCC(=O)C1
N-Boc-3-pyrrolidinone
O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
D-glucose
C[C@H](N)C(=O)O
L-alanine
Cc1ncc(COP(=O)(O)O)c(C=O)c1O
pyridoxal phosphate
CC(C)(C)OC(=O)N1CCC(=O)C1
N-Boc-3-pyrrolidinone
O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
D-glucose
Cc1ncc(COP(=O)(O)O)c(C=O)c1O
pyridoxal phosphate
→
CC(C)(C)OC(=O)N1CCC(N)C1
N-Boc-3-aminopyrrolidine

Reactants

CC(C)(C)OC(=O)N1CCC(=O)C1
N-Boc-3-pyrrolidinone
O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
D-glucose
NC(=O)c1ccc[n+]([C@@H]2O[C@H](COP(=O)(O)OP(=O)(O)OC[C@H]3O[C@@H](n4cnc5c(N)ncnc54)[C@H](O)[C@@H]3O)[C@@H](O)[C@H]2O)c1
NAD+
Cc1ncc(COP(=O)(O)O)c(C=O)c1O
pyridoxal phosphate
CC(C)(C)OC(=O)N1CCC(=O)C1
N-Boc-3-pyrrolidinone
O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
D-glucose
C[C@H](N)C(=O)O
L-alanine
Cc1ncc(COP(=O)(O)O)c(C=O)c1O
pyridoxal phosphate
CC(C)(C)OC(=O)N1CCC(=O)C1
N-Boc-3-pyrrolidinone
O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
D-glucose
Cc1ncc(COP(=O)(O)O)c(C=O)c1O
pyridoxal phosphate

Reagents

None

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    workup.ADDITIONwere added
  2. 2
    workup.ADDITIONwere added
  3. 3
    workup.ADDITIONwere added
  4. 4
    OtherDuring the reaction
  5. 5
    Otherthe reaction liquid
  6. 6
    workup.ALIQUOTwas sampled
  7. 7
    ExtractionFrom the sample, N-Boc-3-aminopyrrolidine was extracted by the addition of ethyl acetate

Procedure

After 2.5 hours in reaction, 0.625 g of N-Boc-3-pyrrolidinone, 0.91 g of D-glucose, 1.8 g of L-alanine, and 3.3 mg of pyridoxal phosphate were added. Further, after five hours in reaction, 0.625 g of N-Boc-3-pyrrolidinone, 0.91 g of D-glucose, and 3.3 mg of pyridoxal phosphate were added. Furthermore, after nine hours in reaction, 0.25 g of N-Boc-3-pyrrolidinone, 0.36 g of D-glucose, 19 mg of NAD+, and 3.3 mg of pyridoxal phosphate were added. During the reaction, the reaction liquid was sampled. From the sample, N-Boc-3-aminopyrrolidine was extracted by the addition of ethyl acetate after basifying the sample with 6 N aqueous solution of sodium hydroxide. The amount of N-Boc-3-aminopyrrolidine produced was measured by analyzing N-Boc-3-aminopyrrolidine under the following GC conditions. Further, by the law of the art, N-Boc-3-aminopyrrolidine thus obtained was acted on by 3,5-dinitrobenzyl chloride to form a dinitrobenzyl derivative. After that, the dinitrobenzyl derivative was analyzed under the following HPLC conditions, whereby the optical purity thereof was measured. In the result, the amount of N-Boc-3-aminopyrrolidine produced after 23 hours in reaction was 2.14 g. The absolute configuration of N-Boc-3-aminopyrrolidine was (S), and the optical purity was 99.4% e.e.

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08168412B2uspto-grants-2012_05