摘要

本論文主要目的是利用在掩飾鄰苯?34a~i進行三環化反應的方法建構雙環[4.1.0]庚烯酮系統39a~i，並將這些具有雙環產物轉變成托酚酮衍生物40, 81。
最初，製備穩定可單離到的各種掩飾鄰苯?並將其與Corey-Chaykovsky試劑進行反應，藉由三環化反應建構雙環[4.1.0]庚烯酮系統。其中，掩飾鄰苯?是一個具有共軛雙烯酮的系統並具有三處親電子中心(圖一) 。一般說來，當Corey-Chaykovsky試劑與掩飾鄰苯?反應時它將偏好立體障礙較小的親電子中心，而研究結果也會因掩飾鄰苯?的取代基位置不同而得到兩種不同的三圓環產物39a~g，39h~i。
環氧化產物76a~b是藉由改變Corey-Chaykovsky試劑當量數而得，獲得兩個不同的產物，其中主要產物76b為Corey-Chaykovsky試劑與羰基進行反應時由立體障礙較小處進入而得。
接著，為了解Corey-Chaykovsky試劑的chemoselectivity，選擇掩飾鄰苯?的二聚合物與Corey-Chaykovsky試劑反應，反應結果得知Corey-Chaykovsky試劑會先於二聚物的羰基進行反應形成環氧化產物77而不會先於α,β-不飽和羰基處進行三環化反應。
最後，選擇幾雙環[4.1.0]庚烯酮產物將其轉換成托酚酮衍生物40, 81。

Abstract

This thesis deals with the synthesis of bicyclo[4.1.0]heptenone systems 39a~i via cyclopropanation reaction of masked o-benzoquinones (MOBs) 34a~i and the subsequent transformation of the obtained bicyclic compounds to corresponding substituted tropolones 40, 81.
Initially a set of stable and isolable MOBs bearing different substitution patterns were prepared. Dimethylsulfoxonium methylide 38 commonly known as Corey-Chaykovsky reagent (CCR) a well-known methylene transfer agent is employed for cyclopropanation reaction of MOBs to furnish bicyclo[4.1.0]heptenone systems of interest. MOB is a conjugated dienone system with ‘THREE’ electrophilic sites (Figure 1). Interestingly, the incoming sulfur ylide (nucleophile) preferred sterically favorable electrophilic site. Thus, two different kinds of cyclopropanation products were obtained 39a~g, 39h~i.
The expoxidation protocol 76a~b of bicyclo[4.1.0]heptenone system was not facial selective though the major product 76bwas obtained by the methylene transfer to the ketone moiety from the other side of the cyclopropane ring due to steric considerations.
Further, to understand the chemoselectivity of the CCR, dimer 77 was utilized. This study revealed the preference of CCR to free ketone functionality to furnish epoxide 77 ather than the α,β-unsaturated ketone group which gives cyclopropane product.
Finally a selected set of bicyclo[4.1.0]heptenone systems upon a three step reaction sequence provided substituted tropolones 40, 81 in good yield.

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