An efficient stereoselective total synthesis of DL-sesquicillin, a glucocorticoid antagonist.
An efficient stereoselective total synthesis of DL-sesquicillin, a glucocorticoid antagonist.
复制标题
DL-倍半西林（一种糖皮质激素拮抗剂）的高效立体选择性全合成。
DOI：
10.1002/1521-3773(20020415)41:8
复制
发表时间：
2002
期刊：
影响因子：
--
通讯作者：
Danishefsky,SamuelJ
中科院分区：
文献类型：
--
作者：
Zhang,Fei;Danishefsky,SamuelJ
首页--期刊主要分类--期刊细介绍--期刊题录与文摘--期刊详细文摘内容2000年，24,477；b)MG Davidson，J.Chem。SoC。化学。交警。1995年，919；c)MG Davidson，S.Lamb，多面体1997，16,4393；d)MG Davidson，KB Dillon，JAK Howard，S.Lamb，MD Roden，J.Organomet。化学。[2]最近的评论见：A)Wa Herrmann，VPW Bohm，CWK GSTˆttmayr，M.Grosche，CP Reisinger，T.Weskamp，J.Organomet。化学。2001年，617,616；b)D.Bourissou，O.Guerret，FP Gabbai，G.Bertrand，Chem.2000年版，100，39；c)AJ Arduengo，行政和预算问题办公室。化学。结果1999，32,913；d)瓦赫尔曼，安徽。化学。2002年，114,1326；Angew。化学。内部艾德[3]AJ Arduengo，SF Gamper，M.Tamm，JC Calabrese，F.Davidson，HA Craig，J.Am化学。SoC。1995年，117,572.[4]a)晶体数据4：C167H229N8O4，无色块尺寸0.2 0.2 0.1mm3，三角，P3≈，a 27.008(9)，c 17.684(9)ä，V11171(8)ä3，Z3，1calcd 1.076 g cm 3.在布鲁克智能衍射仪上收集的数据与莫α辐射(L 0.71073ä)和W扫描在T 100(2)K，2qmax 54.968,121 949反射测量，其中17075独立(RINT 0.0557)，M 0.063 mm±1(无吸收校正)。结构用直接方法(SHELXS-97)[13]求解，F2用全矩阵最小二乘法(SHELXL-97)精化，[13]867个参数，R1 0.0597(11562数据I&>2S(I))，WR2 0.1852(所有数据)。除了那些参与氢键的氢原子被自由和各向同性地精炼外，H原子被放置在计算的位置上，并进行了骑行精炼。晶格正己烷溶剂的位置占有率估计为0.75，并固定在该值。B)5的晶体数据：C33H35N3，尺寸为0.50.3±0.2 mm~3的黄色针，三斜形，P1≈，a 9.663(2)，b 10.578(2)，c 14.967(3)，a 80.60(3)，b 71.68(3)，g 67.72(3)8，V 1342.3(5)ä3，Z 2，1calcd 1.172 cm±3。数据收集在布鲁克智能衍射仪上，具有莫克α辐射(L 0.71073ä)和在T 30(2)K的w扫描，2qmax为54.348，共测得11025次反射，其中5307次独立(RINT为0.0285)，m为0.069 mm±1(无吸收校正)。结构用直接方法(SHELXS-97)[13]求解，F2用全矩阵最小二乘法(SHELXL-97)精化，[13]465个参数，R1 0.0376(4412个数据I&>2S(I))，WR2 0.0991(所有数据)。所有的氢原子都是自由各向同性的。CCDC-161117和CCDC-161118(分别为4和5)包含了本文补充的结晶学数据。这些数据可以通过WWW免费获取。中国疾病预防控制中心。卡姆。交流电。UK/CONTS/RETERVING。或来自剑桥晶体数据中心，地址：英国剑桥CB21EZ联合路12号；传真：(44)1223-336-033；卡姆。交流电。英国)。[5]有关C？H原媛元O氢键几何性质的一般讨论，请参阅：GR Desiraju，T.Steiner，The Share Hond Bond in Structure Chemical and Biology，牛津大学出版社，牛津，1999。另见：T.Steiner，Angew。化学。2002年，114，50；安格鲁。化学。内部艾德2002年，41，48.[6]H.Bock，R.Dienelt，H.SchˆDel，Z.Havlas，J.SoC。化学。交警。1993年，1792年。
Z18515][1] a) MG Davidson, AE Goeta, JAK Howard, S. Lamb, SA Mason, New J. Chem. 2000, 24, 477; b) MG Davidson, J. Chem. Soc. Chem. Commun. 1995, 919; c) MG Davidson, S. Lamb, Polyhedron 1997, 16, 4393; d) MG Davidson, KB Dillon, JAK Howard, S. Lamb, MD Roden, J. Organomet. Chem. 1997, 550, 481.[2] For recent reviews see: a) WA Herrmann, VPW Bohm, CWK Gstˆttmayr, M. Grosche, CP Reisinger, T. Weskamp, J. Organomet. Chem. 2001, 617, 616; b) D. Bourissou, O. Guerret, FP Gabbai, G. Bertrand, Chem. Rev. 2000, 100, 39; c) AJ Arduengo, Acc. Chem. Res. 1999, 32, 913; d) WA Herrmann, Angew. Chem. 2002, 114, 1326; Angew. Chem. Int. Ed. 2002, 41, 1276 (review in this issue).[3] AJ Arduengo, SF Gamper, M. Tamm, JC Calabrese, F. Davidson, HA Craig, J. Am. Chem. Soc. 1995, 117, 572.[4] a) Crystal data for 4: C167H229N8O4, colorless block of dimensions 0.2 Â 0.2 Â 0.1 mm3, trigonal, P3≈, a 27.008 (9), c 17.684 (9) ä, V 11 171 (8) ä3, Z 3, 1calcd 1.076 g cmÀ3. Data collected on a Bruker Smart diffractometer with MoKα radiation (l 0.71073 ä) and w scans at T 100 (2) K, 2qmax 54.968, 121 949 reflections measured, of which 17075 independent (Rint 0.0557), m 0.063 mmÀ1(no absorption correction). Structure solved by direct methods (SHELXS-97)[13] and refined on F 2 by full-matrix least-squares (SHELXL-97),[13] 867 parameters, R1 0.0597 (11562 data I> 2s (I)), wR2 0.1852 (all data). H atoms were placed in calculated positions with a riding refinement, except those involved in hydrogen bonding which were refined freely and isotropically. Site occupancy of lattice hexane solvent was estimated to be 0.75 and fixed at that value. b) Crystal data for 5: C33H35N3, yellow needle of dimensions 0.5 Â 0.3 Â 0.2 mm3, triclinic, P1≈, a 9.663 (2), b 10.578 (2), c 14.967 (3) ä, a 80.60 (3), b 71.68 (3), g 67.72 (3) 8, V 1342.3 (5) ä3, Z 2, 1calcd 1.172 g cmÀ3. Data collected on a Bruker Smart diffractometer with MoKα radiation (l 0.71073 ä) and w scans at T 30 (2) K, 2qmax 54.348, 11 025 reflections measured, of which 5307 independent (Rint 0.0285), m 0.069 mmÀ1 (no absorption correction). Structure solved by direct methods (SHELXS-97)[13] and refined on F 2 by full-matrix least-squares (SHELXL-97),[13] 465 parameters, R1 0.0376 (4412 data I> 2s (I)), wR2 0.0991 (all data). All H atoms were refined freely and isotropically. CCDC-161117 and CCDC-161118 (4 and 5, respectively) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www. ccdc. cam. ac. uk/conts/retrieving. html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax:(44) 1223-336-033; or deposit@ ccdc. cam. ac. uk).[5] For a general discussion of the geometrical properties of CÀH¥¥¥ O hydrogen bonds see: GR Desiraju, T. Steiner, The Weak Hydrogen Bond in Structural Chemistry and Biology, Oxford University Press, Oxford, 1999. See also: T. Steiner, Angew. Chem. 2002, 114, 50; Angew. Chem. Int. Ed. 2002, 41, 48.[6] H. Bock, R. Dienelt, H. Schˆdel, Z. Havlas, J. Chem. Soc. Chem. Commun. 1993, 1792.