Triethyl phosphite → (1S,5R,6S)-7-(diethoxy-phosphoryl)-5-methanesulfonyloxy-7-aza-bicyclo[4.1.0]hept-2-ene-3-carboxylic acid ethyl ester

HRID 1773018Notes

Reaction equation

HRID 1773018 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@@H:10]([O:12][S:13]([CH3:16])(=[O:15])=[O:14])[C@@H:9](OS(C)(=O)=O)[C@H:8]([N:22]=[N+]=[N-])[CH:7]=1)=[O:5])[CH3:2].[P:25]([O:32]CC)([O:29][CH2:30][CH3:31])[O:26][CH2:27][CH3:28]>C1(C)C=CC=CC=1>[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@@H:10]([O:12][S:13]([CH3:16])(=[O:15])=[O:14])[C@@H:9]2[C@@H:8]([N:22]2[P:25]([O:29][CH2:30][CH3:31])([O:26][CH2:27][CH3:28])=[O:32])[CH:7]=1)=[O:5])[CH3:2]

Participants

4

Reactant 2

HCID 31215Triethyl phosphiteHCID 86628951(3R,4S,5R)-3-Azido-4,5-bis-methanesulfonyloxy-cyclohex-1-enecarboxylic acid ethyl ester

Product 1

HCID 44221277(1S,5R,6S)-7-(diethoxy-phosphoryl)-5-methanesulfonyloxy-7-aza-bicyclo[4.1.0]hept-2-ene-3-carboxylic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

(3R,4S,5R)-3-azido-4,5-bis-methanesulfonyloxy-cyclohex-1-enecarboxylic acid ethyl ester (44) was dissolved under argon with stirring in toluene. The clear solution was treated at room temperature with triethyl phosphite and stirred at room temperature for 30 minutes whereby after about 5 minutes gas evolution started. The light yellow reaction mixture was heated to reflux for 6 hours, evaporated at 40° C./60-10 mbar to yield of the crude product (1S,5R,6S)-7-(diethoxy-phosphoryl)-5-methanesulfonyloxy-7-aza-bicyclo[4.1.0]hept-2-ene-3-carboxylic acid ethyl ester (45) as a yellow oil, which was used in the next step without further purification. An analytical sample of (1S,5R,6S)-7-(diethoxy-phosphoryl)-5-methanesulfonyloxy-7-aza-bicyclo[4.1.0]hept-2-ene-3-carboxylic acid ethyl ester was obtained via a silica column chromatography using a 2:1 mixture of toluene and acetone. The combined fractions were evaporated and dried on a rotary evaporator at 40° C./250-10 mbar to obtain 45 as a yellow oil (45).

Workup

  1. temperatureThe light yellow reaction mixture was heated
  2. temperatureto reflux for 6 hours
  3. customevaporated at 40° C./60-10 mbar to yield of the crude product (1S,5R,6S)-7-(diethoxy-phosphoryl)-5-methanesulfonyloxy-7-aza-bicyclo[4.1.0]hept-2-ene-3-carboxylic acid ethyl ester (45) as a yellow oil, which
  4. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-52e56c3ee2a54524bf2dbe54c2c1e93c
Source dataset
uspto-grants-2016_02
Patent number
US09250238B2

Reaction notes

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