Baylis-Hillman 반응을 이용한 Methyl 2-Aroyloxyacrylate 와 2-Alkoxy-3-arylsulfinylmethylquinoline 유도체의 합성

Abstract

Carbon-carbon bond formation is the most important and fundamental reactions in organic chemistry. The development of efficient and selective methods of the construction of carbon-carbon bonds has been continues to be a challenging and exciting endeavor in organic synthesis.

The Baylis– Hillman reaction involves the coupling of activated alkenes with carbon electrophiles under the influence of a Lewis base such as tertiary amine. The Baylis– Hillman reaction has attracted the attention of a number of chemists in recent years, as providing a synthetically useful multifunctional molecule, which has grown from an obscure level to the level of high synthetic popularity.

As a part of group work, the key idea of my research was focused on the Baylis– Hillman reaction followed by manipulation of BH adducts in order to furnish target molecules. The results of researches were expressed in both chapters 1 and 2.

In chapter 1, the treatment of BH adducts with silica gel-supported sodium hypochlorite is an efficient procedure for the synthesis of 2-aroyl-2-methoxycarbonyloxiranes. These can be used for the preparation of methyl 2-aroyloxypropenoates by PPh3 in THF under the reflux condition. These acrylates will be able to apply to various research areas.

In chapter 2, the BH acetate using 2-azidobenzaldehydes with aryl thiols occurred in SN2' fashion to give alkyl 3-(2-azidophenyl)-2-(arylthiomethyl)-propenoates. Allyl aryl sulfides and mCPBA in dichloromethane at 0oC are produced the required key intermediate alkyl 3-(2-azidophenyl)-2-(arylsulfinyl-methyl)propenoates. In all cases, the stereoselectivity was found to be totally Z-selectivity, as determined by 1H NMR analysis of vinylic protons by comparison with literature values. The Staudinger reaction between alkyl 3-(2-azidophenyl)-2-(phenylsulfinylmethyl)propenoates and triphenylphosphine in anhydrous benzene gave the corresponding iminophosphoranes followed by an aza-Wittig reaction at an ester carbonyl group to produce 2-alkoxy-3-aroylsulfinylmethylquinolines with triphenylphosphine oxide.