[(1R,3S,4R,5R,7S,10R,11S,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-13-(anthracene-2-carbonyloxy)-4,11,12,17,24,25,26,28,30-nonahydroxy-18-(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-5-yl]methyl anthracene-2-carboxylate | 1469806-79-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(1R,3S,4R,5R,7S,10R,11S,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-13-(anthracene-2-carbonyloxy)-4,11,12,17,24,25,26,28,30-nonahydroxy-18-(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-5-yl]methyl anthracene-2-carboxylate
• CAS: 1469806-79-8
• 化学式: C₅₄H₅₆O₂₂
• 分子量: 1057.03
• InChiKey: LHGYBABGWCAKQD-DEKCRHBJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  76
• 可旋转键数：
  8
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  329
• 氢给体数：
  10
• 氢受体数：
  22

反应信息

• 作为产物：
  描述：

  2-蒽甲酸 、 cyclo-{->6)-α-D-Glcp-(1->3)-α-D-Glcp-(1->6)-α-D-Glcp-(1->3)-α-D-Glcp-(1->} 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 [(1R,3S,4R,5R,7S,10R,11R,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-13-(anthracene-2-carbonyloxy)-4,11,17,24,25,26,28,30-octahydroxy-5,18-bis(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-12-yl] anthracene-2-carboxylate 、 [(1R,3S,4R,5R,7S,10R,11S,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-4,11,12,13,17,24,25,26,28,30-decahydroxy-18-(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-5-yl]methyl anthracene-2-carboxylate 、 [(1R,3S,4R,5R,7S,10R,11S,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-26-(anthracene-2-carbonyloxy)-4,11,12,17,24,25,28,30-octahydroxy-5,18-bis(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-13-yl] anthracene-2-carboxylate 、 [(1R,3S,4R,5R,7S,10R,11S,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-13-(anthracene-2-carbonyloxy)-4,11,12,17,24,25,26,28,30-nonahydroxy-18-(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-5-yl]methyl anthracene-2-carboxylate 、 [(1R,3S,4R,5R,7S,10R,11S,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-26-(anthracene-2-carbonyloxy)-4,11,12,13,17,24,25,28,30-nonahydroxy-18-(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-5-yl]methyl anthracene-2-carboxylate 、 [(1R,3S,4R,5R,7S,10R,11S,12S,13R,14R,16S,17R,18R,20S,23R,24S,25S,26R,28R,30R)-4,11,12,17,24,25,26,28,30-nonahydroxy-5,18-bis(hydroxymethyl)-2,6,8,15,19,21,27,29-octaoxapentacyclo[21.3.1.13,7.110,14.116,20]triacontan-13-yl] anthracene-2-carboxylate
  参考文献：
  名称：

  Diastereodifferentiating Photocyclodimerization of 2-Anthracenecarboxylates Tethered to a Cyclic Tetrasaccharide Scaffold: Critical Control of Photoreactivity and Stereoselectivity

  摘要：

  From a complex mixture of mono- and di-2-anthracenecarboxylic acid (AC) esters of cyclic nigerosylnigerose (CNN), two monoesters (2(B)) and 6(A)) and four diesters in which AC was introduced on the transannular B/D (2(B)2(D)), adjacent A/B and A/D (6(A)2(B) and 6(A)2(D)), and same B/B (2(B)3(B)) nigerose rings were isolated. Possessing two ACs at distant positions, 2(B)2(D) and 6(A)2(D)) showed negative Cotton effects for the B-1(b) band, the intensities of which were stronger than that of 6(A). 2(B)2(D) and 6(A)2(D) slowly photocyclodimerized to give HH dimers 3* and 4 with 57% and 81% HH selectivity, respectively, which were appreciably higher than that for 6(A) (34%), while the enantiomeric excesses (ee's) of anti-HH dimer 3* were 2% and -18%, respectively. In contrast, 6(A)2(B) and 2(B)3(B) carrying two ACs on adjacent A and B rings or at vicinal positions on the B ring, respectively, exhibited strong positive CD couplets, the amplitudes of which amounted to 97 and 409 M-1 cm(-1), respectively. Upon irradiation, 6(A)2(B) afforded 3* with -62% ee and 4 in 96% combined yield, whereas 2(B)3(B) gave almost exclusively 3* with -99% ee in 96% yield, likely as a result of the introduction of two ACs at the vicinal positions of the rigid CNN scaffold.

  DOI：

  10.1021/jo401977f

文献信息

• Diastereodifferentiating Photocyclodimerization of 2-Anthracenecarboxylates Tethered to a Cyclic Tetrasaccharide Scaffold: Critical Control of Photoreactivity and Stereoselectivity
  作者：Gaku Fukuhara、Tomohiro Nakamura、Yuko Kawanami、Cheng Yang、Tadashi Mori、Hiroyuki Hiramatsu、Yasufumi Dan-oh、Tomoyuki Nishimoto、Kazuo Tsujimoto、Yoshihisa Inoue

  DOI：10.1021/jo401977f

  日期：2013.11.1

  From a complex mixture of mono- and di-2-anthracenecarboxylic acid (AC) esters of cyclic nigerosylnigerose (CNN), two monoesters (2(B)) and 6(A)) and four diesters in which AC was introduced on the transannular B/D (2(B)2(D)), adjacent A/B and A/D (6(A)2(B) and 6(A)2(D)), and same B/B (2(B)3(B)) nigerose rings were isolated. Possessing two ACs at distant positions, 2(B)2(D) and 6(A)2(D)) showed negative Cotton effects for the B-1(b) band, the intensities of which were stronger than that of 6(A). 2(B)2(D) and 6(A)2(D) slowly photocyclodimerized to give HH dimers 3* and 4 with 57% and 81% HH selectivity, respectively, which were appreciably higher than that for 6(A) (34%), while the enantiomeric excesses (ee's) of anti-HH dimer 3* were 2% and -18%, respectively. In contrast, 6(A)2(B) and 2(B)3(B) carrying two ACs on adjacent A and B rings or at vicinal positions on the B ring, respectively, exhibited strong positive CD couplets, the amplitudes of which amounted to 97 and 409 M-1 cm(-1), respectively. Upon irradiation, 6(A)2(B) afforded 3* with -62% ee and 4 in 96% combined yield, whereas 2(B)3(B) gave almost exclusively 3* with -99% ee in 96% yield, likely as a result of the introduction of two ACs at the vicinal positions of the rigid CNN scaffold.