Dipeptidyl peptidase-IV inhibitor-aminotetrahydropyrane derivative
An alkyl and aryl technology, applied in drug combinations, metabolic diseases, endocrine system diseases, etc.
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specific Embodiment approach
[0091] Process 1:
[0092]
[0093] The compound of formula (I) can be prepared according to Scheme 1, and the compound of formula (II) can be prepared with suitable reagents such as sodium triacetoxyborohydride, sodium borohydride, decaborane, sodium cyanoborohydride, etc., in a suitable solvent For example, in N,N-dimethylacetamide, N,N-dimethylmethylamine, dimethyl sulfoxide, ethanol, methanol, toluene, pyridine, dichloromethane, etc., in the presence of the compound of formula (III), Reductive amination occurs to give compounds of formula (IV). Then remove the protecting group PG under suitable conditions and introduce R 1 and / or R 2 (when R 1 and R 2 are not hydrogen at the same time), the compound of formula (I) is obtained.
[0094] Process 2:
[0095]
[0096] The compound of formula (I) can also be prepared according to scheme 2. First, the compound of formula (II) removes the protecting group PG under appropriate conditions, and introduces R 1 and R 2 (...
Embodiment 1
[0100] Embodiment 1: preparation compound 1
[0101]
[0102] Step 1: Preparation of intermediate 1b
[0103]
[0104] 1a (9.0g, 43mmol) and hydrazine hydrochloride (4.5g, 43mmol) were dissolved in absolute ethanol (250ml), stirred at 60°C for 3h, the solvent was distilled off under reduced pressure, and saturated sodium bicarbonate solution (50ml) was added until solid It was completely dissolved, extracted with ethyl acetate, and the obtained organic phase was removed by evaporation under reduced pressure to obtain a white solid 1b (6.3 g, yield 66%) which was used in the next reaction without further purification.
[0105] Step 2: Preparation of intermediate 1c
[0106]
[0107] Dissolve 1b (500mg, 2.23mmol) in 10ml tetrahydrofuran, add 683 microliters of triethylamine, then add 200 microliters of methanesulfonyl chloride, react at room temperature for 2h, remove the solvent under reduced pressure, and perform column chromatography (P: E=1:1) afforded 1c (487 mg,...
Embodiment 2
[0120] Embodiment 2: preparation compound 2
[0121] Step 1: Preparation of intermediate 2a
[0122]
[0123] Dissolve 1c (200 mg, 0.66 mmol) in 5 ml of dichloromethane, then add 1 ml of trifluoroacetic acid, react at room temperature for 2 h, remove the solvent under reduced pressure, neutralize with an appropriate amount of ammonia, remove the water under reduced pressure, and perform column chromatography (2 Chloromethane:methanol=20:1) to obtain 125 mg of oily liquid 2a, yield 63.3%.
[0124] Step 2: Preparation of Intermediate 2b
[0125]
[0126] Dissolve 2a (125mg, 0.42mmol) and 1f (137mg, 0.42mmol) in DMA, place in an ice bath, then add sodium triacetoxyborohydride (131mg, 0.62mmol), react for 2h, then add water After extraction with ethyl acetate, the solvent was removed under reduced pressure, followed by column chromatography to obtain 143 mg of white solid with a yield of 56%.
[0127] Step 3: Preparation of Compound 2
[0128]
[0129] Dissolve 2b in ...
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