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Preparation method for secondary alcohol

A secondary alcohol and compound technology, applied in the field of secondary alcohol preparation

Inactive Publication Date: 2012-07-18
卡莱尔技术创新有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this reaction requires the use of specially designed chiral ligands and expensive ruthenium or rhodium catalysts

Method used

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  • Preparation method for secondary alcohol
  • Preparation method for secondary alcohol
  • Preparation method for secondary alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 3aa to 3a

[0038] Among the above reaction conditions, phenylboronic acid (1a) reacts with aromatic aldehydes, heterocyclic aldehydes and aliphatic aldehydes with various substituents to produce secondary alcohols. Benzaldehyde with electron-withdrawing groups (for example, with 4-NO 2 Substituent (2b), with 4-CHO substituent (2c), with 4-CO 2 Me substituent (2d) and have 4-CF 3 Substituent (2e)) gave diarylcarbinols 3ab-3ae in good yields (89-97%; Table 1 entries 2-5).

[0039] Benzaldehyde derivatives with halogen substituents are also suitable for the catalytic reaction of the present invention. For example substituents 4-F(2f), 3-F(2g), 2-F(2h), 4-Cl(2i) and 4-Br(2j) can react efficiently with phenylboronic acid (1a) to generate relative The diarylmethanols 3af-3aj have good or excellent yields (please refer to Table 1 No. 6-10).

[0040] Similarly, benzaldehyde (2k), 1-napthalaldehyde (1-napthalaldehyde, 2l), and 2-napthalaldehyde (2-napthalaldehyde, 2m) can also undergo additio...

Embodiment 3bd-3id

[0045] In addition, arylboronic acids having various substituents in the present invention can be reacted with methyl 4-formylbenzoate (2d). The substituents of arylboronic acid include 4-Br(1b), 4-F(1c), 4-CHO(1d), 4-Me(1e), 4-OMe(1f), 2-OMe(1g) and 4 -vinyl(1h) can be reacted with 2d to produce substituted diaryl carbinols 3bd-3hd in yields of 93, 93, 84, 92, 97, 96 and 75% (refer to Table 1 No. 20- 26).

[0046] From the above results, it can be seen that the addition reaction of the present invention is widely applicable to various functional groups, such as Br, F, CHO, Me and OMe.

[0047] In addition, this catalytic reaction is also applicable to phenylboronic acids with alkenyl groups. Among them, (E)-styrylboronic acid ((E)-styrylboronic acid, 1i) was reacted with 2d to obtain a secondary alcohol with an allyl group, and the yield was 78% (please refer to No. 27 in Table 1).

Embodiment

[0048] Example: using different catalysts

[0049] in Co(acac) 2 (5mol%), dppe (5mol%) dissolved in THF / CH 3 In CN (1:1), phenylboronic acid (1a) and 4-cyanobenzaldehyde (2a) were reacted at 80° C. for 12 hours to obtain the addition product 3aa with a yield of 96%.

[0050] In this reaction, no additional base was needed, only 1.2 mmol of organoboronic acid was used.

[0051] The above catalytic reactions can also use CoI 2 or CoCl 2 (5mol%) and dppe (5mol%) as catalyst, and use THF as solvent to obtain 3aa, its yield is 9697%, but this time needs to add base K 2 CO 3 (1.5 equivalents) to activate boronic acid.

[0052] enantioselective secondary alcohols

[0053] Please refer to Table 2 and the following reaction formula, another object of the present invention provides a kind of enantioselective preparation method of secondary alcohol, it is by making an organic boronic acid compound 1 and an aldehyde compound 2 in an organic solution Reaction to obtain enantioselec...

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Abstract

The invention relates to a preparation method for secondary alcohol. Cobalt ions and bidentate ligand are utilized to catalyze the addition reaction of organic boric acids and aldehydes, thereby obtaining the medical secondary alcohol. Besides, the invention also discloses an enantioselectivity preparation method for the secondary alcohol. The preparation method for the secondary alcohol has the advantages that the cheap cobalt ions and marketed chiral ligand are used for reacting; various organic boric acids and aldehydes are suitable for the preparation method for the secondary alcohol provided by the invention; and the yield and / or the enantiomer excessive percentage are / is excellent.

Description

technical field [0001] The invention relates to a preparation method of secondary alcohol, in particular to a preparation method of secondary alcohol which uses cobalt ions and ligands to catalyze the addition reaction of organic boric acid and aldehydes. Background technique [0002] Chiral secondary alcohol compounds and their derivatives are common molecular fragments, which widely exist in natural and non-natural molecules with physiological and pharmacological activities. The preparation method of the secondary alcohol compound with substituents mainly uses transition metals to catalyze the addition reaction of organometallic reagents and aldehydes. Among them, organic boronic acid reagents are often used for the reaction due to their high stability to air and moisture, low toxicity, and easy availability. Among the catalysts used, metal complexes such as rhodium, palladium, platinum and nickel can effectively catalyze the addition reaction of organic boric acid and al...

Claims

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Application Information

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IPC IPC(8): C07B41/02C07B53/00C07C253/30C07C255/53C07C201/12C07C205/19C07C45/68C07C45/64C07C47/57C07C67/343C07C67/31C07C69/78C07C29/38C07C33/46C07C33/24C07C33/18C07C41/30C07C41/26C07C43/23C07D213/30C07D307/42C07D333/16C07C33/34B01J31/22B01J31/24
Inventor 郑建鸿卡迪克黄邦齐
Owner 卡莱尔技术创新有限公司
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