樟腦磺內酰胺

樟腦磺內酰胺
	IUPAC名; 2,10-樟腦磺內酰胺; 2,10-Camphorsultam
	系統名; (1S,5R,7R)-10,10-Dimethyl-3-thia-4-azatricyclo[5.2.1.01,5]decane 3,3-dioxide
別名	降冰片烷磺內酰胺、奧波爾策磺內酰胺
識別
CAS號	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
性質
化學式	C10H17NO2S
摩爾質量	215.31 g·mol−1
外觀	白色晶體
密度	1.287 g/cm3
熔點	181 - 183 °C（271 K）
沸點	325 °C（598 K）
折光度n; D	1.567
危險性
主要危害	對呼吸道和呼吸系統有刺激性
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

樟腦磺內酰胺（英語：Camphorsultam）又稱降冰片烷磺內酰胺（英語：bornanesultam）是一種含硫有機化合物。在不對稱有機合成中常作為手性助劑來調控產物對映體選擇性。其外型異構體 (1R)-(+)-樟腦磺內酰胺和(1S)-(-)-樟腦磺內酰胺均有市售。

製備

樟腦磺內酰胺常由樟腦內磺酰亞胺還原得到。該法最初採用雷尼鎳催化加氫還原,^[2]，但現如今已經被氫化鋁鋰還原法取代.^[3]。還原反應具有立體選擇性，即使理論上內型和外形非對映體均可能產生，但實際受制於甲基的空間位阻效應，還原產物只有外形體^[2]。

奧地利化學家沃爾夫岡·奧波爾策（Wolfgang Oppolzer）以及其同事首次開發了氫化鋁鋰還原法製備樟腦磺內酰胺，並首次將其運用到不對稱合成中，因此樟腦磺內酰胺有時又被稱為奧波爾策磺內酰胺（Oppolzer's sultam）^[4]^[5]。

用途

基於分子中的N原子可以進行取代得到系列衍生物，加之手性分子骨架構象難以變化的剛性結構，使得樟腦磺內酰胺是一種很好的手性助劑，在有機合成中可調控產物立體構型。比如大環酯肽抗生素Manzacidin B的立體選擇性合成就用到了樟腦磺內酰胺^[6]。此外，樟腦磺內酰胺作為手性助劑在米高反應^[7]、克萊森重排^[8]和環加成反應^[9]中均能得到很高的產物立體選擇性，這使得人們可以更好地控制反應並生成特定所需產物。如果反應底物配有兩種手性助劑，其之間的協同作用可以進一步提高立體選擇性^[10]。

基於該特點，樟腦磺內酰胺可作為「手性探針」分子來確定化合物的絕對構型^[11]。

參考文獻

^ 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]. （原始內容存檔於2021-09-10）（英語）.
^ ^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] （頁面存檔備份，存於互聯網檔案館）
^ Archived copy (PDF). [2013-07-29]. （原始內容 (PDF)存檔於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]. （原始內容存檔於2021-09-10）（英語）.

[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] （頁面存檔備份，存於互聯網檔案館）

[5] Archived copy (PDF). [2013-07-29]. （原始內容 (PDF)存檔於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.

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