Camphorsultam, also known as bornanesultam, is a crystalline solid primarily used as a chiral auxiliary in the synthesis of other chemicals with a specific desired stereoselectivity. Camphorsultam is commercially available in both enantiomers of its exo forms: (1R)-(+)-2,10-camphorsultam and (1S)-(−)-2,10-camphorsultam.
Camphorsultam is synthesized by reduction of camphorsulfonylimine. This reaction was originally performed as a catalytic hydrogenation using Raney Nickel,[2] but the modern preparation instead uses lithium aluminium hydride for the reduction.[3] These reductive methods are stereoselective: although both the endo and exo diastereomeric forms are theoretically possible, only the exo isomer is actually produced due to steric effects of one of the methyl groups.[2] Camphorsultam is often referred to as Oppolzer's sultam in reference to Wolfgang Oppolzer and colleagues, who developed the lithium aluminium hydride approach to this compound and pioneered its use in asymmetric synthesis.[4][5]
Usesedit
Due to its ability to form derivatives through its nitrogen atom and the structural rigidity of its chirality, camphorsultam is often used in reactions as a chiral auxiliary in order to allow a reaction to proceed with very specific stereoselectivity. During the synthesis of Manzacidin B, camphorsultam is used in order to obtain the desired stereoselective product.[6] During a Michael reaction,[7] a Claisen rearrangement,[8] or a cycloaddition reaction[9] camphorsultam is able to confer a great deal of stereoselectivity. This allows for more control over the reactions and the creation of very specific desired products. Stereoselectivity can be further increased if substrates are equipped with two chiral auxiliaries, acting in a cooperative fashion.[10]
Camphorsultam also has applications in determining a compound's absolute stereochemistry. For that reason, it is sometimes referred to as a "chiral probe".
Referencesedit
^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.
^ abShriner, R. L.; Shotton, J. A.; Sutherland, H. (1938). "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. 60 (11): 2794. doi:10.1021/ja01278a072.
^Weismiller, Michael C.; Towson, James C.; Davis, Franklin A. (1990). "(−)-D-2,10-Camphorsultam". Organic Syntheses. 69: 154; Collected Volumes, vol. 8, p. 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]
^(PDF). Archived from the original (PDF) on 2010-06-26. Retrieved 2013-07-29.{{cite web}}: CS1 maint: archived copy as title (link)
^Shinada, Tetsuro; Oe, Kentaro; Ohfune, Yasufumi (2012). "Efficient Total Synthesis of Manzacidin B". Tetrahedron Letters. 53 (26): 3250–3253. doi:10.1016/j.tetlet.2012.04.042.
^Tsai, Wen Jiuan; Lin, Yi-Tsong; Uang, Biing-Jiun (1994). "Asymmetric Michael Addition of Thiols to (1R,2R,4R)-(–)-2,10-N-Enoylcamphorsultam". Tetrahedron. 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 (2012). "Asmmetric Construction of All-Carbon Quaternary Stereocenters by Chiral Auxiliary Mediated Claisen Rearrangement and Total Synthesis of (+)-Bakuchiol". Molecules. 17 (11): 13330–13344. doi:10.3390/molecules171113330. PMC6268616. PMID 23138536.
^Romanski, Jan; Nowak, Piotr; Chapuis, Christian; Jurczak, Janusz (2011). "Total synthesis of (5S)-dihydroyashabushiketol". Tetrahedron: Asymmetry. 22 (7): 787–790. doi:10.1016/j.tetasy.2011.04.014.
^Romanski, Jan; Nowak, Piotr; Maksymiuk, Anna; Chapuis, Christian; Jurczak, Janusz (2013). "Diastereoselective 1,3-dipolar cycloadditions of both electronically modified phenyl-nitrile oxides and stilbenes". RSC Advances. 3 (45): 23105–23118. Bibcode:2013RSCAd...323105R. doi:10.1039/C3RA41718B.
January 01, 1970
camphorsultam, also, known, bornanesultam, crystalline, solid, primarily, used, chiral, auxiliary, synthesis, other, chemicals, with, specific, desired, stereoselectivity, commercially, available, both, enantiomers, forms, camphorsultam, camphorsultam, names, . Camphorsultam also known as bornanesultam is a crystalline solid primarily used as a chiral auxiliary in the synthesis of other chemicals with a specific desired stereoselectivity Camphorsultam is commercially available in both enantiomers of its exo forms 1R 2 10 camphorsultam and 1S 2 10 camphorsultam Camphorsultam Names IUPAC name 2 10 Camphorsultam Systematic IUPAC name 1S 5R 7R 10 10 Dimethyl 3 thia 4 azatricyclo 5 2 1 01 5 decane 3 3 dioxide Other names Camphorsultam Bornanesultam Oppolzer s Sultam 10 2 Camphorsultam 1S 2 10 Camphorsultam 3aS 6R 7aR 8 8 Dimethylhexahydro 3a 6 methano 2 1 benzisothiazole 2 2 dioxide exo 10 2 Bornanesultam Identifiers CAS Number 108448 77 7 1 N PubChem 3D model JSmol Interactive image ChemSpider 628224 PubChem CID 719751 InChI InChI 1S 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 s1Key DPJYJNYYDJOJNO NRPADANISA NInChI 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 s1Key DPJYJNYYDJOJNO NRPADANIBE SMILES CC1 C H 2CC C 13CS O O N C H 3C2 C Properties Chemical formula C 10H 17N O 2S Molar mass 215 31 g mol 1 Appearance White crystalline solid Density 1 287 g cm3 Melting point 181 to 183 C 358 to 361 F 454 to 456 K Boiling point 325 C 617 F 598 K Refractive index nD 1 567 Hazards Occupational safety and health OHS OSH Main hazards Irritating to respiratory system and respiratory tract Flash point 105 3 C 221 5 F 378 4 K Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox referencesSynthesis edit nbsp Camphorsultam is synthesized by reduction of camphorsulfonylimine This reaction was originally performed as a catalytic hydrogenation using Raney Nickel 2 but the modern preparation instead uses lithium aluminium hydride for the reduction 3 These reductive methods are stereoselective although both the endo and exo diastereomeric forms are theoretically possible only the exo isomer is actually produced due to steric effects of one of the methyl groups 2 Camphorsultam is often referred to as Oppolzer s sultam in reference to Wolfgang Oppolzer and colleagues who developed the lithium aluminium hydride approach to this compound and pioneered its use in asymmetric synthesis 4 5 Uses editDue to its ability to form derivatives through its nitrogen atom and the structural rigidity of its chirality camphorsultam is often used in reactions as a chiral auxiliary in order to allow a reaction to proceed with very specific stereoselectivity During the synthesis of Manzacidin B camphorsultam is used in order to obtain the desired stereoselective product 6 During a Michael reaction 7 a Claisen rearrangement 8 or a cycloaddition reaction 9 camphorsultam is able to confer a great deal of stereoselectivity This allows for more control over the reactions and the creation of very specific desired products Stereoselectivity can be further increased if substrates are equipped with two chiral auxiliaries acting in a cooperative fashion 10 Camphorsultam also has applications in determining a compound s absolute stereochemistry For that reason it is sometimes referred to as a chiral probe References edit 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 a b Shriner R L Shotton J A Sutherland H 1938 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 60 11 2794 doi 10 1021 ja01278a072 Weismiller Michael C Towson James C Davis Franklin A 1990 D 2 10 Camphorsultam Organic Syntheses 69 154 Collected Volumes vol 8 p 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 Archived copy PDF Archived from the original PDF on 2010 06 26 Retrieved 2013 07 29 a href Template Cite web html title Template Cite web cite web a CS1 maint archived copy as title link Shinada Tetsuro Oe Kentaro Ohfune Yasufumi 2012 Efficient Total Synthesis of Manzacidin B Tetrahedron Letters 53 26 3250 3253 doi 10 1016 j tetlet 2012 04 042 Tsai Wen Jiuan Lin Yi Tsong Uang Biing Jiun 1994 Asymmetric Michael Addition of Thiols to 1R 2R 4R 2 10 N Enoylcamphorsultam Tetrahedron 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 2012 Asmmetric Construction of All Carbon Quaternary Stereocenters by Chiral Auxiliary Mediated Claisen Rearrangement and Total Synthesis of Bakuchiol Molecules 17 11 13330 13344 doi 10 3390 molecules171113330 PMC 6268616 PMID 23138536 Romanski Jan Nowak Piotr Chapuis Christian Jurczak Janusz 2011 Total synthesis of 5S dihydroyashabushiketol Tetrahedron Asymmetry 22 7 787 790 doi 10 1016 j tetasy 2011 04 014 Romanski Jan Nowak Piotr Maksymiuk Anna Chapuis Christian Jurczak Janusz 2013 Diastereoselective 1 3 dipolar cycloadditions of both electronically modified phenyl nitrile oxides and stilbenes RSC Advances 3 45 23105 23118 Bibcode 2013RSCAd 323105R doi 10 1039 C3RA41718B Retrieved from https en wikipedia org w index php title Camphorsultam amp oldid 1141999810, wikipedia, wiki, book, books, library,
