樟脑磺内酰胺

樟脑磺内酰胺
	IUPAC名; 2,10-樟脑磺内酰胺; 2,10-Camphorsultam
	系统名; (1S,5R,7R)-10,10-Dimethyl-3-thia-4-azatricyclo[5.2.1.01,5]decane 3,3-dioxide
别名	降冰片烷磺内酰胺、奥波尔策磺内酰胺
识别
CAS号	108448-77-7 [PubChem]
PubChem	719751
ChemSpider	628224
SMILES	CC1([C@H]2CC[C@@]13CS(=O)(=O)N[C@H]3C2)C;
InChI	1/C10H17NO2S/c1-9(2)7-3-4-10(9)6-14(12,13)11-8(10)5-7/h7-8,11H,3-6H2,1-2H3/t7-,8-,10-/m0/s1;
InChIKey	DPJYJNYYDJOJNO-NRPADANIBE
性质
化学式	C10H17NO2S
摩尔质量	215.31 g·mol−1
外观	白色晶体
密度	1.287 g/cm3
熔点	181 - 183 °C（271 K）
沸点	325 °C（598 K）
折光度n; D	1.567
危险性
主要危害	对呼吸道和呼吸系统有刺激性
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

樟脑磺内酰胺（英語：Camphorsultam）又称降冰片烷磺内酰胺（英語：bornanesultam）是一种含硫有机化合物。在不对称有机合成中常作为手性助剂来调控产物对映体选择性。其外型异构体 (1R)-(+)-樟脑磺内酰胺和(1S)-(-)-樟脑磺内酰胺均有市售。

制备

樟脑磺内酰胺常由樟脑内磺酰亚胺还原得到。该法最初采用雷尼镍催化加氢还原,^[2]，但现如今已经被氢化铝锂还原法取代.^[3]。还原反应具有立体选择性，即使理论上内型和外形非对映体均可能产生，但实际受制于甲基的空间位阻效应，还原产物只有外形体^[2]。

奥地利化学家沃尔夫冈·奥波尔策（Wolfgang Oppolzer）以及其同事首次开发了氢化铝锂还原法制备樟脑磺内酰胺，并首次将其运用到不对称合成中，因此樟脑磺内酰胺有时又被称为奥波尔策磺内酰胺（Oppolzer's sultam）^[4]^[5]。

用途

基于分子中的N原子可以进行取代得到系列衍生物，加之手性分子骨架构象难以变化的刚性结构，使得樟脑磺内酰胺是一种很好的手性助剂，在有机合成中可调控产物立体构型。比如大环酯肽抗生素Manzacidin B的立体选择性合成就用到了樟脑磺内酰胺^[6]。此外，樟脑磺内酰胺作为手性助剂在迈克尔反应^[7]、克莱森重排^[8]和环加成反应^[9]中均能得到很高的产物立体选择性，这使得人们可以更好地控制反应并生成特定所需产物。如果反应底物配有两种手性助剂，其之间的协同作用可以进一步提高立体选择性^[10]。

基于该特点，樟脑磺内酰胺可作为“手性探针”分子来确定化合物的绝对构型^[11]。

参考文献

^ Chambers, Michael. ChemIDplus - 0108448777 - DPJYJNYYDJOJNO-UHFFFAOYSA-N - (2S)-Bornane-10,2-sultam - Similar structures search, synonyms, formulas, resource links, and other chemical information.. chem.nlm.nih.gov. [2024-07-27]. （原始内容存档于2021-09-10）（英语）.
^ ^2.0 ^2.1 Shriner, R. L.; Shotton, J. A.; Sutherland, H. Anomalous Mutarotation of Salts of Reychler's Acid. VI. Synthesis and Structure of the Sultam of 2-(N-Methylamino)-d-camphane-10-sulfonic Acid. J. Am. Chem. Soc. 1938, 60 (11): 2794. doi:10.1021/ja01278a072.
^ (1990) "(−)-D-2,10-Camphorsultam". Org. Synth. 69: 154; Coll. Vol. 8: 110.
^ Oppolzer, Wolfgang."Camphor as a natural source of chirality in asymmetric synthesis".Pure Appl. Chem., Vol. 62, No. 7, pp. 1241-1250, (1990).[1] （页面存档备份，存于互联网档案馆）
^ Archived copy (PDF). [2013-07-29]. （原始内容 (PDF)存档于2010-06-26）.
^ Shinada, Tetsuro; Oe, Kentaro; Ohfune, Yasufumi. Efficient Total Synthesis of Manzacidin B. Tetrahedron Letters. 2012, 53 (26): 3250–3253. doi:10.1016/j.tetlet.2012.04.042.
^ Tsai, Wen Jiuan; Lin, Yi-Tsong; Uang, Biing-Jiun. Asymmetric Michael Addition of Thiols to (1R,2R,4R)-(–)-2,10-N-Enoylcamphorsultam. Tetrahedron. 1994, 5 (7): 1195–1198. doi:10.1016/0957-4166(94)80155-X.
^ Takao, Ken-ichi; Sakamoto, Shu; Touati, Marianne Ayaka; Kusakawa, Yusuke; Tadano, Kin-ichi. Asmmetric Construction of All-Carbon Quaternary Stereocenters by Chiral Auxiliary Mediated Claisen Rearrangement and Total Synthesis of (+)-Bakuchiol. Molecules. 2012, 17 (11): 13330–13344. PMC 6268616 . PMID 23138536. doi:10.3390/molecules171113330 .
^ Romanski, Jan; Nowak, Piotr; Chapuis, Christian; Jurczak, Janusz. Total synthesis of (5S)-dihydroyashabushiketol. Tetrahedron: Asymmetry. 2011, 22 (7): 787–790. doi:10.1016/j.tetasy.2011.04.014.
^ Romanski, Jan; Nowak, Piotr; Maksymiuk, Anna; Chapuis, Christian; Jurczak, Janusz. Diastereoselective 1,3-dipolar cycloadditions of both electronically modified phenyl-nitrile oxides and stilbenes. RSC Advances. 2013, 3 (45): 23105–23118. Bibcode:2013RSCAd...323105R. doi:10.1039/C3RA41718B.
^ Nobuyuki Harada , Tomomi Soutome , Shinji Murai，Hisashi Uda. A chiral probe useful for optical resolution and X-ray crystallographic determination of the absolute stereochemistry of carboxylic acids. Tetrahedron: Asymmetry. 1993, 4 (8): 1755–1758. doi:10.1016/S0957-4166(00)80409-7.

[1] Chambers, Michael. ChemIDplus - 0108448777 - DPJYJNYYDJOJNO-UHFFFAOYSA-N - (2S)-Bornane-10,2-sultam - Similar structures search, synonyms, formulas, resource links, and other chemical information.. chem.nlm.nih.gov. [2024-07-27]. （原始内容存档于2021-09-10）（英语）.

[shriner-2] 2.0 ^2.1 Shriner, R. L.; Shotton, J. A.; Sutherland, H. Anomalous Mutarotation of Salts of Reychler's Acid. VI. Synthesis and Structure of the Sultam of 2-(N-Methylamino)-d-camphane-10-sulfonic Acid. J. Am. Chem. Soc. 1938, 60 (11): 2794. doi:10.1021/ja01278a072.

[organic-3] (1990) "(−)-D-2,10-Camphorsultam". Org. Synth. 69: 154; Coll. Vol. 8: 110.

[4] Oppolzer, Wolfgang."Camphor as a natural source of chirality in asymmetric synthesis".Pure Appl. Chem., Vol. 62, No. 7, pp. 1241-1250, (1990).[1] （页面存档备份，存于互联网档案馆）

[5] Archived copy (PDF). [2013-07-29]. （原始内容 (PDF)存档于2010-06-26）.

[6] Shinada, Tetsuro; Oe, Kentaro; Ohfune, Yasufumi. Efficient Total Synthesis of Manzacidin B. Tetrahedron Letters. 2012, 53 (26): 3250–3253. doi:10.1016/j.tetlet.2012.04.042.

[7] Tsai, Wen Jiuan; Lin, Yi-Tsong; Uang, Biing-Jiun. Asymmetric Michael Addition of Thiols to (1R,2R,4R)-(–)-2,10-N-Enoylcamphorsultam. Tetrahedron. 1994, 5 (7): 1195–1198. doi:10.1016/0957-4166(94)80155-X.

[8] Takao, Ken-ichi; Sakamoto, Shu; Touati, Marianne Ayaka; Kusakawa, Yusuke; Tadano, Kin-ichi. Asmmetric Construction of All-Carbon Quaternary Stereocenters by Chiral Auxiliary Mediated Claisen Rearrangement and Total Synthesis of (+)-Bakuchiol. Molecules. 2012, 17 (11): 13330–13344. PMC 6268616 . PMID 23138536. doi:10.3390/molecules171113330 .

[9] Romanski, Jan; Nowak, Piotr; Chapuis, Christian; Jurczak, Janusz. Total synthesis of (5S)-dihydroyashabushiketol. Tetrahedron: Asymmetry. 2011, 22 (7): 787–790. doi:10.1016/j.tetasy.2011.04.014.

[10] Romanski, Jan; Nowak, Piotr; Maksymiuk, Anna; Chapuis, Christian; Jurczak, Janusz. Diastereoselective 1,3-dipolar cycloadditions of both electronically modified phenyl-nitrile oxides and stilbenes. RSC Advances. 2013, 3 (45): 23105–23118. Bibcode:2013RSCAd...323105R. doi:10.1039/C3RA41718B.

[11] Nobuyuki Harada , Tomomi Soutome , Shinji Murai，Hisashi Uda. A chiral probe useful for optical resolution and X-ray crystallographic determination of the absolute stereochemistry of carboxylic acids. Tetrahedron: Asymmetry. 1993, 4 (8): 1755–1758. doi:10.1016/S0957-4166(00)80409-7.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]