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Gold-catalyzed cyclization reactions...

Tarselli, Michael Andrew.

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Gold-catalyzed cyclization reactions of allenes.

紀錄類型:	書目-語言資料,印刷品 : Monograph/item
正題名/作者:	Gold-catalyzed cyclization reactions of allenes./
作者:	Tarselli, Michael Andrew.
面頁冊數:	150 p.
附註:	Source: Dissertation Abstracts International, Volume: 70-04, Section: B, page: 2313.
Contained By:	Dissertation Abstracts International70-04B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3352662
ISBN:	9781109106329

Gold-catalyzed cyclization reactions of allenes.
Tarselli, Michael Andrew.

Gold-catalyzed cyclization reactions of allenes. - 150 p.

Source: Dissertation Abstracts International, Volume: 70-04, Section: B, page: 2313.

Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2009.

Cycloisomerization is a so-called "atom-economic" tool to produce complex carbocycles from simple precursors. Gold catalysis is an extension of cation-olefin cyclization utilizing Pt2+ that had been a previous focus of our group. As a homogeneous metal catalyst, gold - especially in the (I) oxidation state - is highly carbophilic, exhibits high functional group tolerance, and is not inhibited by trace moisture or air. This combination of attributes is ideal for use of gold as a catalytic C-C bond-forming tool.

ISBN: 9781109106329Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Gold-catalyzed cyclization reactions of allenes.
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245 1 0 $a Gold-catalyzed cyclization reactions of allenes.
300 $a 150 p.
500 $a Source: Dissertation Abstracts International, Volume: 70-04, Section: B, page: 2313.
500 $a Adviser: Michel R. Gagne.
502 $a Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2009.
520 $a Cycloisomerization is a so-called "atom-economic" tool to produce complex carbocycles from simple precursors. Gold catalysis is an extension of cation-olefin cyclization utilizing Pt2+ that had been a previous focus of our group. As a homogeneous metal catalyst, gold - especially in the (I) oxidation state - is highly carbophilic, exhibits high functional group tolerance, and is not inhibited by trace moisture or air. This combination of attributes is ideal for use of gold as a catalytic C-C bond-forming tool.
520 $a Eneallene cycloisomerization catalyzed by gold(I) yields vinylcyclohexenes in a rare example of 6-membered ring formation. However, enantioselective synthesis with gold is challenging due to the linear bonding geometries observed for gold(I) salts. A sufficiently bulky chiral di-gold complex with judicious counterion choice produces the desired vinylcyclohexene in up to 72% yield (77% ee).
520 $a Allenes tethered to an electron-rich aromatic ring in place of an alkene partner cyclize to form tetrahydronaphthalene skeletons, even at 1 mol% catalyst loading in commercial-grade solvent. This catalysis was accelerated by more electrophilic phosphite ligands, along with a larger, weakly coordinated counterion (-SbF6). Yields range from 59-94%. If the tethered arene is non-nucleophilic (Ph) or strongly deactivating ( p-NO2), selective hydration of the allene to a methyl ketone is preferred, which provides both a mechanistic rationale and a benchmark for arene nucleophilicity that correlates well with literature. More electrophilic catalyst precursors are able to catalyze the intermolecular addition of electron-rich arenes to allenes, although the scope of this transformation was significantly more limited (9 examples, 22-90% yield). This reaction does not proceed with coordinating arenes and sterically demanding allenes.
520 $a Cascade cyclization of allenyl epoxides proceeds rapidly under gold(I) catalysis to produce polyethers remniscient of those found in marine and soil polyethers. Initial attempts to cyclize simple allenyl mono- or bis-epoxides led to complex product mixtures, but use of a hydroxyl "trapping group" yields polycycles in 35-65% yield. Carbocation stability (3° > 2° > 1°) controls ring formation in the cascade; the resultant polycycles appear to be stereospecific with respect to initial epoxide geometry. The cyclization can be extended to form both fused and linked polyethers from properly-substituted polyepoxides.
590 $a School code: 0153.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Organic. $3 516206
690 $a 0488
690 $a 0490
710 2 $a The University of North Carolina at Chapel Hill. $b Chemistry. $3 1021872
773 0 $t Dissertation Abstracts International $g 70-04B.
790 1 0 $a Gagne, Michel R., $e advisor
790 1 0 $a Brookhart, Maurice $e committee member
790 1 0 $a Johnson, Jeffrey $e committee member
790 1 0 $a Waters, Marcey $e committee member
790 1 0 $a Lin, Wenbin $e committee member
790 $a 0153
791 $a Ph.D.
792 $a 2009
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3352662