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Stereocontrolled Formation of Bicycl...

MacMillan, David William Cross,

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Stereocontrolled Formation of Bicyclic Tetrahydrofurans and Enantioselective Total Synthesis of Eunicelling Diterpenes /

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Stereocontrolled Formation of Bicyclic Tetrahydrofurans and Enantioselective Total Synthesis of Eunicelling Diterpenes // David William Cross MacMillan.
作者:	MacMillan, David William Cross,
面頁冊數:	1 electronic resource (196 pages)
附註:	Source: Dissertations Abstracts International, Volume: 58-03, Section: B.
Contained By:	Dissertations Abstracts International58-03B.
標題:	Organic chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9621533
ISBN:	9798460498949

Stereocontrolled Formation of Bicyclic Tetrahydrofurans and Enantioselective Total Synthesis of Eunicelling Diterpenes /
MacMillan, David William Cross,

Stereocontrolled Formation of Bicyclic Tetrahydrofurans and Enantioselective Total Synthesis of Eunicelling Diterpenes /David William Cross MacMillan. - 1 electronic resource (196 pages)

Source: Dissertations Abstracts International, Volume: 58-03, Section: B.

Part I. A practical process for the stereocontrolled preparation of oxobicyclo (3.3.0) octanes, oxobicyclo (3.4.0) nonanes and oxobicyclo (3.5.0) decanes from readily available allylic diol and carbonyl components has been developed. Bicyclic tetrahydrofuran formation can occur by Lewis acid promoted reorganization of cycloalkenyl acetals, or alternatively by acid promoted condensation of cyclic allylic diols with aryl or αβ-unsaturated aldehydes. Exclusive formation of all-cis-tetrahydrofuran diastereomers can be effected by (i) condensation-rearrangement of cyclic allylic diols with aryl or αβ-unsaturated aldehydes, (ii) rearrangement of syn acetals at all temperatures or (iii) rearrangement of anti acetals at high temperature. Formation of trans-tetrahydrofuran diastereomers can be accomplished with high stereoselectivity by reorganization of anti acetals at low temperatures. Several mechanistic rationales for the formation of trans-tetrahydrofuran isomers are presented. The utility of this new bicyclic tetrahydrofuran synthesis for constructing complex oxacyclics as well as for the asymmetric synthesis of marine metabolites such as eunicellin diterpenes is disclosed in part II.Part II. The first total synthesis of the marine metabolites (−)-7-deacetoxyalcyonin acetate (25) and eunicellin triol 22 were accomplished in a convergent fashion from (S)-carvone and (S)-glycidol. The central step of both syntheses was the Lewis acid promoted Prins-pinacol condensation-rearrangement of dienyl diol 87 with the αβ-unsaturated aldehyde 88 to form the hexahydroisobenzofuran 86 in 79% yield (equation 2.1). These syntheses in their present form could be utilized for production of 22, 25 and other eunicellin diterpenes for pharmacological and structural studies.

English

ISBN: 9798460498949Subjects--Topical Terms:

523952
Organic chemistry.
Subjects--Index Terms:

Stereocontrolled

Stereocontrolled Formation of Bicyclic Tetrahydrofurans and Enantioselective Total Synthesis of Eunicelling Diterpenes /
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245 1 0 $a Stereocontrolled Formation of Bicyclic Tetrahydrofurans and Enantioselective Total Synthesis of Eunicelling Diterpenes / $c David William Cross MacMillan.
264 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 1996
300 $a 1 electronic resource (196 pages)
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500 $a Source: Dissertations Abstracts International, Volume: 58-03, Section: B.
500 $a Publisher info.: Dissertation/Thesis.
500 $a Advisors: Overman, Larry E. Committee members: Moore, Harold W.; Shea, Kenneth J.
502 $b Ph.D. $c University of California, Irvine $d 1996.
520 $a Part I. A practical process for the stereocontrolled preparation of oxobicyclo (3.3.0) octanes, oxobicyclo (3.4.0) nonanes and oxobicyclo (3.5.0) decanes from readily available allylic diol and carbonyl components has been developed. Bicyclic tetrahydrofuran formation can occur by Lewis acid promoted reorganization of cycloalkenyl acetals, or alternatively by acid promoted condensation of cyclic allylic diols with aryl or αβ-unsaturated aldehydes. Exclusive formation of all-cis-tetrahydrofuran diastereomers can be effected by (i) condensation-rearrangement of cyclic allylic diols with aryl or αβ-unsaturated aldehydes, (ii) rearrangement of syn acetals at all temperatures or (iii) rearrangement of anti acetals at high temperature. Formation of trans-tetrahydrofuran diastereomers can be accomplished with high stereoselectivity by reorganization of anti acetals at low temperatures. Several mechanistic rationales for the formation of trans-tetrahydrofuran isomers are presented. The utility of this new bicyclic tetrahydrofuran synthesis for constructing complex oxacyclics as well as for the asymmetric synthesis of marine metabolites such as eunicellin diterpenes is disclosed in part II.Part II. The first total synthesis of the marine metabolites (−)-7-deacetoxyalcyonin acetate (25) and eunicellin triol 22 were accomplished in a convergent fashion from (S)-carvone and (S)-glycidol. The central step of both syntheses was the Lewis acid promoted Prins-pinacol condensation-rearrangement of dienyl diol 87 with the αβ-unsaturated aldehyde 88 to form the hexahydroisobenzofuran 86 in 79% yield (equation 2.1). These syntheses in their present form could be utilized for production of 22, 25 and other eunicellin diterpenes for pharmacological and structural studies.
546 $a English
590 $a School code: 0030
650 4 $a Organic chemistry. $3 523952
650 4 $a Physical chemistry. $3 1981412
650 4 $a Molecular chemistry. $3 1071612
653 $a Stereocontrolled
653 $a Chemical synthesis
653 $a Bicyclic tetrahydrofuran
690 $a 0490
690 $a 0431
690 $a 0494
710 2 $a University of California, Irvine. $e degree granting institution. $3 3821728
720 1 $a Overman, Larry E. $e degree supervisor.
773 0 $t Dissertations Abstracts International $g 58-03B.
790 $a 0030
791 $a Ph.D.
792 $a 1996
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