本篇論文主要是探討具有L-式異葡萄糖(gulose)為基本單元的博菜黴素(bleomycin)之雙醣體和藻酸(alginate)的多醣體之合成研究，包括開發新穎的方法來製備非天然的L-式異葡萄糖(gulose)。在雙糖體的合成方面以購得的二丙酮 □-D-葡萄糖54經由三個合成步驟合成L式的愛杜糖(idose)衍生物60，產率有51%。接者選擇性將第二號碳的立體中心翻轉產生L式異葡萄醣的衍生物(gulose) 75作為醣供給體(glycosyl aceptor)。另外，以購得的1,6-anhdro-□-D-mannopyranose 73 為起始物進行選擇性在第二號氧和第四號氧的位置引進苯甲酯的保護基，進而在第三號氧的位置進行反應得到酯類的衍生物77。進而經由三個合成步驟(acetolysis, anomeric deacetylation和imidiation)可以得到imidate的衍生物 80 作為醣;供予體(glycosyl donor)，和醣接受體 75在路易士酸(TMSOTf)催化下，醣供給體和醣接受體產生化學反應產生雙糖體81，產率為82%，進一步進行兩個合成步驟得到博菜黴素雙醣體的衍生物83(57%)。
在藻酸多醣體的合成方面，選用維他命C為起始物經由四個合成步驟(氫化、isopropylidenation、用DIABL進行還原和酸性水解)可以得到異葡萄醣的衍生物 88，產率為56%。接者只分別需要四個和五個合成步驟，分別得到醣供予體 108 和醣接受體104。醣供予體108和醣接受體104在路易士酸的催化下進行醣鏈結反應生成□-連結的雙醣體 109，產率有70%，接者進行兩個化學反應得以得到化合物112(79%)。重複此四個步驟(imidation-glycosylation-acetolysis-removal of anomeric acetate)一到兩次，可以得到三醣衍生物116和四醣的衍生物120，接者個別進行四個步驟的官能機轉換可以順利得到目標分子130-132。

This thesis is concerned with the syntheses of bleomycin-disaccharide and alginate oligosaccharides that both contain the rare L-gulopyranosyl sugars as basic components. 1,6-Anhydro-□-L-idopyranose 60, obtained from diacetone □-D-glucose 54 in three steps in 51% overall yield, was converted to the 1,6-anhydro-□-L-gulopyranosyl sugar 75 (72%) via one-pot O2-triflation and O3,O4-dibenzoylation followed by nucleophilic substitution with NaNO2 at C2. Consecutive O2,O4-dibenzoylation and O3-carbonylation of commercially available 1,6-anhydro-□-D-mannopyranose 73 provided the ester 77 (48%), which underwent acetolysis, anomeric deacetylation, and imidation to yield the corresponding imidate 80 (61%) in three steps. Coupling of 80 with 75 in the presence of TMSOTf led to the disaccharide 81 (82%), which was subjected to acetolysis followed by nucleophilic displacement with ammonia to afford the bleomycin-disaccharide moiety 83 in 57% yield.
For the synthesis of alginate oligosaccharides, a four-stepped conversion of vitamin C via hydrogenation, isopropylidenation, DIBAL reduction, and acidic hydrolysis gave 1,6-anhydro-□-L-gulopyranose 88 in 56% overall yield, which was transformed into the donor 108 (81%) and the acceptor 104 (61%) in four and five steps, respectively. TMSOTf-activated coupling of 108 and 104 furnished the □-linked disaccharide 109 (70%), which was opened under acetolysis conditions followed by anomeric deacetylation to yield the 1-alcohol 112 (79%). The elongation cycle was then repeated twice to assemble the tri- and tetrasaccharides 116 and 120 through a four-stepped protocol [imidation-glycosylation- acetolysis-anomeric deacetylation], respectively. Anomeric allylation of 112, 116, and 120, individually, led to the □-linked ethers 121-123, which underwent sequential deacetylation, TEMPO oxidation, and reduction to afford alginate oligosaccharides 130-132, respectively.

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