臺灣博碩士論文加值系統

本論文介紹了三種手性配體的合成及其在2,3-二氫呋喃環化中的應用。它們是樟腦
基聯吡啶，蒎烯基聯吡啶和2 - （（芐氧基）二苯基甲基）四氫噻吩。 這些配體按照已
知的方法製備，並且它們用於在烯酮和溴乙酸乙酯存在下的對映選擇性製備2,3-二氫呋
喃。 用各種醛製備相應的呋喃。 給出最佳對映體選擇性的配體是具有59％ee的順式異
構體的2 - （（芐氧基）二苯基甲基）四氫噻吩和2,3-二氫呋喃的反式異構體的54％
ee。

This thesis describes the synthesis of three kinds of chiral ligand and their application
in the cyclization of 2,3-dihydrofuran. They are camphor-based bipyridine, pinene-based
bipyridine and 2-((benzyloxy)diphenylmethyl)tetrahydrothiophene. These ligands were
prepared followed the known procedure, and they were used for the enantioselective
preparation of 2,3-dihydrofuran in the present of enone and ethyl bromoacetate. The various
aldehydes were used to prepare the corresponding of furan. The ligand that give the best
enantioselectivity is 2-((benzyloxy)diphenylmethyl)tetrahydrothiophene with 59% ee for cis
isomer and 54% ee for trans isomer of 2,3-dihydrofuran

Abstract……………………………………………………………………………………....iv
摘要……………………………………………………………………………………………v Acknowledgement…………………………………………………………………………...vi
Contents……………………………………………………………………………………..vii
List of schemes......................................................................................................................... ix
List of tables.............................................................................................................................. x
Abbreviations .......................................................................................................................... xi
I. Introduction ..................................................................................................................... 1
1.1 The synthesis of 2,3-dihydrofurans ............................................................................. 1
II. Result and discussion ...................................................................................................... 3
2.1 Synthesis of camphor-based bipyridine ...................................................................... 3
2.2 Application in asymmetric reaction of trans-2,3-dihydrofuran using camphor-based bipyridine ............................................................................................................................... 4
2.3 Synthesis of pinene-based bipyridine .......................................................................... 4
2.4 Application in asymmetric reaction of trans/cis-2,3-dihydrofuran using pinene-based bipyridine ............................................................................................................................... 5
2.5 Synthesis of (thiolan-2-yl)diphenylmethanol .............................................................. 8
2.6 Catalyst screening and optimization of 2,3-dihydrofuran using 2-((benzyloxy)diphenylmethyl)tetrahydrothiophene ................................................................. 9
III. Conclusion ..................................................................................................................... 13
IV. Experimental section .................................................................................................... 15
4.1 Instrument Section..................................................................................................... 15
4.2 Synthesis of camphor-based bipyiridine ................................................................... 15
4.2.1 Synthesis of ethyl trifluoroacetate ..................................................................... 15
viii
4.2.2 Synthesis of (1R,4R)-3-trifluoroacetyl-1,7,7-methylbicyclo[2.2.1]heptane-2-one……….. ...................................................................................................................... 16
4.2.3 Synthesis of (R)-(1β,4β)-3-methylene-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one……. ........................................................................................................................... 16
4.2.4 Synthesis of 1-(2-oxo-2-(pyridine-2-yl)ethyl)pyridine-1-ium; iodide ............... 17
4.2.5 Synthesis of 8,9,9-trimethyl-2(pyridin-2-yl)-5,6,7,8-tetrahydro-5,8-methanoquinoline ............................................................................................................. 18
4.3 Synthesis of pinene-based bipyridine ........................................................................ 19
4.3.1 Optical purification of 91% α-(+)-pinene (2,6,6-trimethyl-bicyclo[3.1.1]hept-2-ene…….. ........................................................................................................................... 19
4.3.2 Synthesis of (–)-pinocarvone ............................................................................. 20 4.3.3 Synthesis of (5S,7R)-(-)-5,6,7,8,-tetrahydro-6,6-dimethyl-2-(pyridin-2-yl)-5,7-methanoquinoline ............................................................................................................. 20
4.3.4 Synthesis of alkyl substituted pinene-based bipyridine ..................................... 21
4.3.5 Synthesis of pinene-based bipyridine salt .......................................................... 25
4.4 Synthesis of (S)-(+)-2-((benzyloxy)diphenylmethyl)tetrahydrothiophene ............... 26
4.4.1 Synthesis of 5-bromo-1,1-diphenylpentan-1-ol ................................................. 26
4.4.2 Synthesis of 5,5-diphenyl-4-pentenyl bromide .................................................. 27
4.4.3 Synthesis of (R)-(+)-3-(3-bromopropyl)-2,2-diphenyloxirane .......................... 28
4.4.4 Synthesis of (S)-(−)-thiolan-2-yl)diphenylmethanol.......................................... 29
4.4.5 Synthesis of (S)-(+)-2-((benzyloxy)diphenylmethyl)tetrahydrothiophene ........ 29
4.5 Synthesis of 2,3-dihydrofuran ................................................................................... 30
4.5.1 Synthesis of 3-benzylidene-2,4-pentanedione ................................................... 30
4.5.2 Synthesis of 2,3-dihydrofuran ............................................................................ 32
V. References ...................................................................................................................... 39

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