Substituted Benzenes: The Reddy Synthesis of Isofregenedadiol

Chemical Laboratory ◽

University Of Technology ◽

Simple Protocol ◽

Peking University ◽

The University ◽

Technological University

Jianbo Wang of Peking University (Org. Lett. 2011, 13, 4988) and Patrick Y. Toullec and Véronique Michelet of Chimie ParisTech (Org. Lett. 2011, 13, 6086) developed conditions for the electrophilic acetoxylation of a benzene derivative 1. Seung Hwan Cho and Sukbok Chang of KAIST (J. Am. Chem. Soc. 2011, 133, 16382) and Brenton DeBoef of the University of Rhode Island (J. Am. Chem. Soc. 2011, 133, 19960) devised protocols for the electrophilic imidation of a benzene derivative 3. Vladimir V. Grushin of ICIQ Tarragona devised (J. Am. Chem. Soc. 2011, 133, 10999) a simple protocol for the cyanation of a bromobenzene 6 to the nitrile 7. Hua-Jian Xu of the Hefei University of Technology (J. Org. Chem. 2011, 76, 8036) and Myung-Jong Jin of Inha University (Org. Lett. 2011, 13, 5540) established conditions for the efficient Heck coupling of a chlorobenzene 8. Jacqueline E. Milne of Amgen/Thousand Oaks reduced (J. Org. Chem. 2011, 76, 9519) the adduct from the addition of 11 to 12 to deliver the phenylacetic acid 13. Jeffrey W. Bode of ETH Zurich effected (Angew. Chem. Int. Ed. 2011, 50, 10913) Friedel-Crafts alkylation of 14 with the hydroxamate 15 to give the meta product 16. B.V. Subba Reddy of the Indian Institute of Chemical Technology, Hyderabad took advantage (Tetrahedron Lett. 2011, 52, 5926) of the directing ability of the amide to effect selective ortho acetoxylation of 17. Similarly, Frederic Fabis of the Université de Caen Basse-Normandie used (J. Org. Chem. 2011, 76, 6414) the methoxime of 19 to direct ortho bromination, leading to 20. Teck-Peng Loh of Nanyang Technological University showed (Chem. Commun. 2011, 47, 10458) that the carbamate of 21 directed ortho C–H functionalization to give the ester 23. Yoichiro Kuninobu and Kazuhiko Takai of Okayama University rearranged (Chem. Commun. 2011, 47, 10791) the allyl ester 24 directly to the ortho-allylated acid 25. Youhong Hu of the Shanghai Institute of Materia Medica (J. Org. Chem. 2011, 76, 8495) and Graham J. Bodwell of Memorial University (J. Org. Chem. 2011, 76, 9015) condensed a chromene 26 with a nucleophile 27 to give the arene 28. C.V. Ramana of the National Chemical Laboratory prepared (Tetrahedron Lett. 2011, 52, 4627) the arene 31 by condensing 29 with 30 with high regioselectivity.

Diels-Alder Cycloaddition: (+)-Armillarivin (Banwell), Gelsemiol (Gademann), (+)-Frullanolide (Liao), Myceliothermophin A (Uchiro), Peribysin E (Reddy), Caribenol A (Li/Yang)

Organic Synthesis ◽

10.1093/oso/9780190200794.003.0081 ◽

2015 ◽

Author(s):

Douglass F. Taber

Keyword(s):

Elevated Pressure ◽

Diels Alder ◽

Cope Rearrangement ◽

Chemical Laboratory ◽

Enantiomerically Pure ◽

Peking University ◽

National University ◽

Diastereoselective Addition ◽

Martin G. Banwell of the Australian National University prepared (Org. Lett. 2013, 15, 1934) the enantiomerically pure diol 1 by fermentation of the aromatic precursor. Diels-Alder addition of cyclopentenone 2 proceeded well at elevated pressure to give 3, the precursor to (+)-armillarivin 4. Karl Gademann of the University of Basel found (Chem. Eur. J. 2013, 19, 2589) that the Diels-Alder addition of 6 to 5 proceeded best without solvent and with Cu catalysis to give 7. Reduction under free radical conditions led to gelsemiol 8. Chun-Chen Liao of the National TsingHua University carried out (Org. Lett. 2013, 15, 1584) the diastereoselective addition of 10 to 9. A later oxy-Cope rearrangement established the octalin skeleton of (+)-frullanolide 12. D. Srinivasa Reddy of CSIR-National Chemical Laboratory devised (Org. Lett. 2013, 15, 1894) a strategy for the construction of the angularly substituted cis-fused aldehyde 15 based on Diels-Alder cycloaddition of 14 to the diene 13. Further transformation led to racemic peribysin-E 16. An effective enantioselective catalyst for dienophiles such as 14 has not yet been developed. Hiromi Uchiro of the Tokyo University of Science prepared (Tetrahedron Lett. 2012, 53, 5167) the bicyclic core of myceliothermophin A 19 by BF3•Et2O-promoted cyclization of the tetraene 17. The single ternary center of 17 mediated the formation of the three new stereogenic centers of 18, including the angular substitution. En route to caribenol A 22, Chuang-Chuang Li and Zhen Yang of the Peking University Shenzen Graduate School assembled (J. Org. Chem. 2013, 78, 5492) the triene 20 from two enantiomerically pure precursors. Inclusion of the radical inhibitor BHT sufficed to suppress competing polymerization, allowing clean cyclization to 21. Methylene blue has also been used (J. Am. Chem. Soc. 1980, 102, 5088) for this purpose.

Diels–Alder Cycloaddition: Pancratistatin (Cho), Nootkatone (Reddy), Platensimycin (Zhang/Lee), Scabronine G (Nakada), Isoglaziovianol (Trauner)

Organic Synthesis ◽

10.1093/oso/9780190646165.003.0077 ◽

2017 ◽

Author(s):

Douglass F. Taber

Keyword(s):

Aldol Condensation ◽

Diels Alder ◽

Cancer Center ◽

Columbia University ◽

Chemical Laboratory ◽

Intramolecular Cycloaddition ◽

Enantiomerically Pure ◽

Peking University ◽

Samuel J. Danishefsky of Columbia University and the Memorial Sloan-Kettering Cancer Center made (Proc. Natl. Acad. Sci. 2013, 110, 10904) the unexpected observation that methylation of the enolate derived from conjugate addition to the readily-prepared 1 followed by intramolecular alkene metathesis led to the trans fused ketone 2. This can be contrasted to the diastereo- and regioisomer 3, the product from Diels-Alder cycloaddition of 2-methylcyclohexenone to isoprene. The trans ring fusion of 2 is particularly significant because ozonolysis followed by aldol condensation would deliver the angularly-methylated trans-fused 6/5 C–D ring system of the steroids and related natural products. Cheon-Gyu Cho of Hanyang University added (Org. Lett. 2013, 15, 5806) the activated dienophile 4 to the dienyl lactone to give, after oxidation, the dibromide 5. Debromination followed by oxidation led to the antineoplastic lactam pancratistatin 6. D. Srinivasa Reddy of CSIR-National Chemical Laboratory Pune devised (J. Org. Chem. 2013, 78, 8149) a cascade protocol of Diels-Alder cycloaddition of 8 to the diene 7, followed by intramolecular aldol condensation, to give the enone 9. Oxidative manipulation followed by methylenation completed the synthesis of the commercially important grapefruit flavor nootkatone 10. Xinhao Zhang and Chi-Sing Lee of the Peking University Shenzen Graduate School uncovered (J. Org. Chem. 2013, 78, 7912) another cascade transformation, intermolecular addition of 11 to 12 followed by intramolecular Conia-ene cyclization, to give the tricyclic 13. Further manipulation led to an established intermediate for the total synthesis of platensimycin 14. Masahisa Nakada of Waseda University prepared (Angew. Chem. Int. Ed. 2013, 52, 7569) the enantiomerically-pure allene 15. Oxidation of the phenol to the monoketal of the cyclohexadienone set the stage for intramolecular cycloaddition to give 16. Oxidative cleavage followed by intramolecular alkene metathesis led to (+)-scabronine G 17. Dirk Trauner of the University of Munich assembled (Org. Lett. 2013, 15, 4324) the enantiomerically-pure alcohol 18. Oxidation gave the quinone, leading to intramolecular Diels–Alder cycloaddition. The free alcohol then added to the exocyclic alkene of that product, to give, after further oxidation, the ether 19. Deprotection followed by reduction then completed the synthesis of (−)-isoglaziovianol 20.

Functional Group Protection: The Pohl Synthesis of β-1,4-Mannuronate Oligomers

Organic Synthesis ◽

10.1093/oso/9780190646165.003.0015 ◽

2017 ◽

Author(s):

Douglass F. Taber

Keyword(s):

Iron Catalyst ◽

Gold Catalyst ◽

State University ◽

Allyl Ester ◽

Chemical Laboratory ◽

Benzyl Ethers ◽

Institute Of Technology ◽

Tokyo Medical ◽

D. Srinivasa Reddy of the National Chemical Laboratory converted (Org. Lett. 2015, 17, 2090) the selenide 1 to the alkene 2 under ozonolysis conditions. Takamitsu Hosoya of the Tokyo Medical and Dental University found (Chem. Commun. 2015, 51, 8745) that even highly strained alkynes such as 4 can be generated from a sulfinyl vinyl triflate 3. An alkyne can be protected as the dicobalt hexacarbonyl complex. Joe B. Gilroy and Mark S. Workentin of the University of Western Ontario found (Chem. Commun. 2015, 51, 6647) that following click chemistry on a non-protected distal alkyne, deprotection of 5 to 6 could be effected by exposure to TMNO. Stefan Bräse of the Karlsruhe Institute of Technology and Irina A. Balova of Saint Petersburg State University showed (J. Org. Chem. 2015, 80, 5546) that the bend of the Co complex of 7 enabled ring-closing metathesis, leading after deprotection to 8. Morten Meldal of the University of Copenhagen devised (Eur. J. Org. Chem. 2015, 1433) 9, the base-labile protected form of the aldehyde 10. Nicholas Gathergood of Dublin City University and Stephen J. Connon of the University of Dublin developed (Eur. J. Org. Chem. 2015, 188) an imidazolium catalyst for the exchange deprotection of 11 to 13, with the inexpensive aldehyde 12 as the acceptor. Peter J. Lindsay-Scott of Eli Lilly demonstrated (Org. Lett. 2015, 17, 476) that on exposure to KF, the isoxazole 14 unraveled to the nitrile 15. Masato Kitamura of Nagoya University observed (Tetrahedron 2015, 71, 6559) that the allyl ester of 16 could be removed to give 17, with the other alkene not affected. Benzyl ethers are among the most common of alcohol protecting groups. Yongxiang Liu and Maosheng Cheng of Shenyang Pharmaceutical University showed (Adv. Synth. Catal. 2015, 357, 1029) that 18 could be converted to 19 simply by exposure to benzyl alcohol in the presence of a gold catalyst. Reko Leino of Åbo Akademi University developed (Synthesis 2015, 47, 1749) an iron catalyst for the reductive benzylation of 20 to 21. Related results (not illustrated) were reported (Org. Lett. 2015, 17, 1778) by Chae S. Yi of Marquette University.

Developments in Alkene Metathesis

Organic Synthesis ◽

10.1093/oso/9780199764549.003.0024 ◽

2011 ◽

Author(s):

Douglass Taber

Keyword(s):

Large Scale ◽

Cross Coupling ◽

Chemical Laboratory ◽

Metal Centers ◽

University Of Pittsburgh ◽

University Of Technology ◽

Alternative Approach ◽

Catalyzed Reactions ◽

Alkene metathesis has been extended to increasingly complex starting materials and products. Nitriles are good donors to coordinatively-unsaturated transition metal centers, so tend to inhibit the reaction. Ren He of Dalian University of Technology has found (Tetrahedron Lett. 2007, 48, 4203) that inclusion of the loosely-coordinating 2-methyl pyridine in the reaction enables facile cross-coupling with acrylonitrile 2. Although crosscoupling with (Z, Z)-sorbate is not efﬁcient, Dennis P. Curran of the University of Pittsburgh has shown (Organic Lett. 2007, 9, 5) that cross-coupling with (E, Z)-sorbate 5 works well. For large scale work, he has developed a Hoveyda-type catalyst with a perﬂuoro tail, that is recoverable in 70% recrystallized yield from the reaction mixture. Shigefumi Kuwahara of Tohoku University has reported (Tetrahedron Lett. 2007, 48, 3163) a practical alternative for direct metathesis to deliver (E, E)-dienyl esters. Continuing the investigation of tandem Ru-catalyzed reactions, Marc L. Snapper of Boston College effected (Organic Lett. 2007, 9, 1749) metathesis with methacrolein 8a, then added Ph3P and diazoacetate, to give the diene 11. A range of common Ru catalysts worked well for this transformation. In an alternative approach to trisubstituted alkene construction, Stellios Arseniyadis and Janine Cossy of ESPCI Paris have demonstrated (Organic Lett. 2007, 9, 1695) that inclusion of Cl-catecholborane 14 allows clean cross metathesis with the lactone 13. The construction of tetrasubstituted alkenes has been more challenging. Yann Schrodi of Materia, Inc. (Organic Lett. 2007, 9, 1589) has described a catalyst 17 that is particularly effective. Complex 17 was superior to a catalyst reported (Organic Lett. 2007, 9, 1339) shortly earlier by Robert H. Grubbs of Caltech. Debendra K. Mohapatra of the National Chemical Laboratory, Pune, and Professor Grubbs, in a new approach to macrocyclic stereocontrol, have made (Tetrahedron Lett. 2007, 48, 2621) the remarkable observation that the cyclization of the bis ether 19a gave 20 in a 9:1 E / Z ratio, while cyclization of the diol 9b gave only Z - 21. Oligomer formation can often compete in such medium ring-forming reactions. Deryn E. Fogg of the University of Ottawa has raised (J. Am. Chem. Soc. 2007, 129, 1024) the cautionary (but happy!) observation that while the cyclization, for instance, of 22 proceeded efficiently to give 23, at an intermediate point in the transformation the product was more than half oligomer.

Functionalization of C-H Bonds: The Baran Synthesis of Dihydroxyeudesmane

Organic Synthesis ◽

10.1093/oso/9780199764549.003.0016 ◽

2011 ◽

Author(s):

Douglass Taber

Keyword(s):

Columbia University ◽

Chemical Laboratory ◽

Du Bois ◽

Rh Catalyst ◽

Hydride Abstraction ◽

Mcgill University ◽

Radical Removal ◽

The University ◽

Useful Yield

Arumugam Sudalai of the National Chemical Laboratory, Pune reported (Tetrahedron Lett. 2008, 49, 6401) a procedure for hydrocarbon iodination. With straight chain hydrocarbons, only secondary iodination was observed. Chao-Jun Li of McGill University uncovered (Adv. Synth. Cat. 2009, 351, 353) a procedure for direct hydrocarbon amination, converting cyclohexane 1 into the amine 3. Justin Du Bois of Stanford University established (Angew. Chem. Int. Ed. 2009, 48, 4513) a procedure for alkane hydroxylation, converting 4 selectively into the alcohol 6. The oxirane 8 usually also preferentially ozidizes methines, hydroxylating steroids at the C-14 position. Ruggero Curci of the University of Bari found (Tetrahedron Lett. 2008, 49, 5614) that the substrate 7 showed some C-14 hydroxylation, but also a useful yield of the ketone 9. The authors suggested that the C-7 acetoxy group may be deactivating the C-14 C-H. C-H bonds can also be converted directly to carbon-carbon bonds. Mark E. Wood of the University of Exeter found (Tetrahedron Lett. 2009, 50, 3400) that free-radical removal of iodine from 10 followed by intramolecular H-atom abstraction in the presence of the trapping agent 11 delivered 12 with good diastereo control. Professor Li observed (Angew. Chem. Int. Ed. 2008, 47, 6278) that under Ru catalysis, hydrocarbons such as 13 could be directly arylated. He also established (Tetrahedron Lett. 2008, 49, 5601) conditions for the direct aminoalkylation of hydrocarbons such as 13, to give 17. Huw M. L. Davies of Emory University converted (Synlett 2009, 151) the ester 4 to the homologated diester 19 in preparatively useful yield using the diazo ester 18, the precursor to a selective, push-pull stabilized carbene. Intramolecular bond formation to an unactivated C-H can be even more selective. Guoshen Liu of the Shanghai Institute of Organic Chemistry developed (Organic Lett. 2009, 11, 2707) an oxidative Pd system that cyclized 20 to the seven-membered ring lactam 21 . Professor Du Bois devised (J. Am. Chem. Soc. 2008 , 130, 9220) a Rh catalyst that effected allylic amination of 22, to give 23 with substantial enantiocontrol. Dalibor Sames of Columbia University designed (J. Am. Chem. Soc. 2009, 131, 402) a remarkable cascade approach to C-H functionalization. Exposure of 24 to Lewis acid led to intramolecular hydride abstraction. Cyclization of the resulting stabilized carbocation delivered the tetrahydropyan 25 with remarkable diastereocontrol.

Substituted Benzenes: The Saikawa/Nakata Synthesis of Kendomycin

Organic Synthesis ◽

10.1093/oso/9780199965724.003.0062 ◽

2013 ◽

Author(s):

Douglass F. Taber

Keyword(s):

Alkyl Iodide ◽

Benzene Derivative ◽

State University ◽

One Pot ◽

Aryl Iodide ◽

Peking University ◽

Cu Catalyst ◽

San Diego State University ◽

University Of Massachusetts ◽

Jianbo Wang of Peking University described (Angew. Chem. Int. Ed. 2010, 49, 2028) the Au-promoted bromination of a benzene derivative such as 1 with N-bromosuccinimide. In a one-pot procedure, addition of a Cu catalyst followed by microwave heating delivered the aminated product 2. Jian-Ping Zou of Suzhou University and Wei Zhang of the University of Massachusetts, Boston, observed (Tetrahedron Lett. 2010, 51, 2639) that the phosphonylation of an arene 3 proceeded with substantial ortho selectivity. Yonghong Gu of the University of Science and Technology, Hefei, showed (Tetrahedron Lett. 2010, 51, 192) that an arylpropanoic acid 6 could be ortho hydroxylated with PIFA to give 7. Louis Fensterbank, Max Malacria, and Emmanuel Lacôte of UMPC Paris found (Angew. Chem. Int. Ed. 2010, 49, 2178) that a benzoic acid could be ortho aminated by way of the cyano amide 8. Daniel J. Weix of the University of Rochester developed (J. Am. Chem. Soc. 2010, 132, 920) a protocol for coupling an aryl iodide 10 with an alkyl iodide 11 to give 12. Professor Wang devised (Angew. Chem. Int. Ed. 2010, 49, 1139) a mechanistically intriguing alkyl carbonylation of an iodobenzene 10. This is presumably proceeding by way of the intermediate diazo alkane. Usually, benzonitriles are prepared by cyanation of the halo aromatic. Hideo Togo of Chiba University established (Synlett 2010, 1067) a protocol for the direct electrophilic cyanation of an electron-rich aromatic 15. Thomas E. Cole of San Diego State University observed (Tetrahedron Lett. 2010, 51, 3033) that an alkyl dimethyl borane, readily prepared by hydroboration of the alkene with BCl3 and Et3 SiH, reacted with benzoquinone 17 to give 18. Presumably this transformation could also be applied to substituted benzoquinones. When a highly substituted benzene derivative is needed, it is sometimes more economical to construct the aromatic ring. Joseph P. A. Harrity of the University of Sheffield and Gerhard Hilt of Philipps-Universität Marburg showed (J. Org. Chem. 2010, 75, 3893) that the Co-catalyzed Diels-Alder cyloaddition of alkynyl borinate 21 with a diene 20 proceeded with high regiocontrol, to give, after oxidation, the aryl borinate 22.

Organic Functional Group Conversion

Organic Synthesis ◽

10.1093/oso/9780199965724.003.0005 ◽

2013 ◽

Author(s):

Douglass F. Taber

Keyword(s):

Hong Kong ◽

Allylic Alcohol ◽

Primary Alcohols ◽

Chemical Laboratory ◽

University Of Texas ◽

University Of Wisconsin ◽

Pan American ◽

Acetate Formation ◽

Pradeep Kumar of the National Chemical Laboratory, Pune, developed (Tetrahedron Lett. 2010, 51, 744) a new procedure for the conversion of an alcohol 1 to the inverted chloride 3. Michel Couturier of OmegaChem devised (J. Org. Chem. 2010, 75, 3401) a new reagent for the conversion of an alcohol 4 to the inverted fluoride 6. For both reagents, primary alcohols worked as well. Patrick H. Toy of the University of Hong Kong showed (Synlett 2010, 1115) that diethyl-lazodicarboxylate (DEAD) could be used catalytically in the Mitsunobu coupling of 7. Employment of 8 minimized competing acetate formation. In another application of hyper-valent iodine chemistry, Jaume Vilarrasa of the Universitat de Barcelona observed (Tetrahedron Lett. 2010, 51, 1863) that the Dess-Martin reagent effected the smooth elimination of a pyridyl selenide 10. Ken-ichi Fujita and Ryohei Yamaguchi of Kyoto University extended (Org. Lett. 2010, 12, 1336) the “borrowed hydrogen” approach to effect conversion of an alcohol 12 to the sulfonamide 13. Dan Yang, also of the University of Hong Kong, developed (Org. Lett. 2010, 12, 1068, not illustrated) a protocol for the conversion of an allylic alcohol to the allylically rearranged sulfonamide. Shu-Li You of the Shanghai Institute of Organic Chemistry used (Org. Lett. 2010, 12, 800) an Ir catalyst to effect rearrangement of an allylic sulfinate 14 to the sulfone. Base-mediated conjugation then delivered 15. K. Rama Rao of the Indian Institute of Chemical Technology, Hyderabad, devised (Tetrahedron Lett. 2010, 51, 293) a La catalyst for the conversion of an iodoalkene 16 to the alkenyl sulfide 17. Alkenyl selenides could also be prepared. James M. Cook of the University of Wisconsin, Milwaukee, described (Org. Lett. 2010, 12, 464, not illustrated) a procedure for coupling alkenyl iodides and bromides with N-H heterocycles and phenols. Hansjörg Streicher of the University of Sussex showed (Tetrahedron Lett. 2010, 51, 2717) that under free radical conditions, the carboxylic acid derivative 18 could be decarboxylated to the alkenyl iodide 19. Bimal K. Banik of the University of Texas–Pan American found (Synth. Commun. 2010, 40, 1730) that water was an effective solvent for the microwave-mediated addition of a secondary amine 21 to a Michael acceptor 20.

Functional Group Transformation: The Castle Synthesis of Celogentin C

Organic Synthesis ◽

10.1093/oso/9780199965724.003.0004 ◽

2013 ◽

Author(s):

Douglass F. Taber

Keyword(s):

Allylic Alcohol ◽

Efficient Reduction ◽

Simple Protocol ◽

Peking University ◽

Celogentin C ◽

Purdue University ◽

Institute Of Technology ◽

Tertiary Amides ◽

The University ◽

Functional Group Transformation

Mark Cushman of Purdue University found (J. Org. Chem. 2010, 75, 3507) that a benzylic methyl ether 1 could be converted to the aldehyde 2 by N -bromosuccinimide. Two equivalents of NBS gave the methyl ester. Ning Jiao of Peking University used (Organic Lett. 2010, 12, 2888) NaN3 followed by DDQ to oxidize a benzylic halide 3 to the nitrile 4. Hugues Miel of Almac Sciences oxidized (Tetrahedron Lett. 2010, 51, 3216) the ketone 5 to the nitro derivative 6. The oxidative conversion of the nitro compound 7 to the ketone 8 described (Tetrahedron Lett. 2009, 50, 6389) by Vera L. Patrocinio Pereira of the Universidade Federal do Rio de Janeiro proceeded without epimerization. Sundarababu Baskaran of the Indian Institute of Technology Madras established (Angew. Chem. Int. Ed. 2010, 49, 804) that oxidative cleavage of the benzylidene acetal 9 delivered 10 with high regioselectivity. The intramolecular alkene dihydroxylation of 11 originated (Angew. Chem. Int. Ed. 2010, 49, 4491) by Erik J. Alexanian of the University of North Carolina gave 12 with high diastereocontrol. Ruimao Hua of Tsinghua University took advantage (J. Org. Chem. 2010, 75, 2966) of the H-donor properties of DMF to develop an efficient reduction of the alkyne 13 to the alkyne 14 . Alejandro F. Barrero of the University of Granada developed (J. Am. Chem. Soc. 2010, 132, 254) Ti (III) conditions for the reduction of the allylic alcohol 15 to the terminal alkene 16. Isolated alkenes were stable to these conditions. P. Veeraraghavan Ramachandran, also of Purdue University, effected (Tetrahedron Lett. 2010, 51, 3167) reductive amination of 17 to 18 using the now readily available NH3 - BH3 . Bin Ma and Wen-Cherng Lee of BiogenIdec developed (Tetrahedron Lett. 2010, 51, 385) a simple protocol for the conversion of an acid 19 to the free amine 20. Marc Lemaire of Université Lyons 1 established (Tetrahedron Lett. 2010, 51, 2092) that the silane 22 reduced primary, secondary, and tertiary amides to the aldehydes.

Organocatalyzed C–C Ring Construction: The Mihovilovic Synthesis of Piperenol B

Organic Synthesis ◽

10.1093/oso/9780190646165.003.0072 ◽

2017 ◽

Author(s):

Douglass F. Taber

Keyword(s):

State University ◽

Air Oxidation ◽

Microbial Oxidation ◽

Max Planck ◽

Chemical Laboratory ◽

Northwestern University ◽

National University ◽

The University ◽

Oregon State University

M. Kevin Brown of Indiana University prepared (J. Am. Chem. Soc. 2015, 137, 3482) the cyclobutane 3 by the organocatalyzed addition of 2 to the alkene 1. Karl Anker Jørgensen of Aarhus University assembled (J. Am. Chem. Soc. 2015, 137, 1685) the complex cyclobutane 7 by the addition of 5 to the acceptor 4, followed by condensation with the phosphorane 6. Zhi Li of the National University of Singapore balanced (ACS Catal. 2015, 5, 51) three enzymes to effect enantioselective opening of the epoxide 8 followed by air oxidation to 9. Gang Zhao of the Shanghai Institute of Organic Chemistry and Zhong Li of the East China University of Science and Technology added (Org. Lett. 2015, 17, 688) 10 to 11 to give 12 in high ee. Akkattu T. Biju of the National Chemical Laboratory combined (Chem. Commun. 2015, 51, 9559) 13 with 14 to give the β-lactone 15. Paul Ha-Yeon Cheong of Oregon State University and Karl A. Scheidt of Northwestern University reported (Chem. Commun. 2015, 51, 2690) related results. Dieter Enders of RWTH Aachen University constructed (Chem. Eur. J. 2015, 21, 1004) the complex cyclopentane 20 by the controlled combination of 16, 17, and 18, followed by addition of the phosphorane 19. Derek R. Boyd and Paul J. Stevenson of Queen’s University Belfast showed (J. Org. Chem. 2015, 80, 3429) that the product from the microbial oxidation of 21 could be protected as the acetonide 22. Ignacio Carrera of the Universidad de la República described (Org. Lett. 2015, 17, 684) the related oxidation of benzyl azide (not illustrated). Manfred T. Reetz of the Max-Planck-Institut für Kohlenforschung and the Philipps-Universität Marburg found (Angew. Chem. Int. Ed. 2014, 53, 8659) that cytochrome P450 could oxidize the cyclohexane 23 to the cyclohexanol 24. F. Dean Toste of the University of California, Berkeley aminated (J. Am. Chem. Soc. 2015, 137, 3205) the ketone 25 with 26 to give 27. Benjamin List, also of the Max-Planck-Institut für Kohlenforschung, reported (Synlett 2015, 26, 1413) a parallel investigation. Philip Kraft of Givaudan Schweiz AG and Professor List added (Angew. Chem. Int. Ed. 2015, 54, 1960) 28 to 29 to give 30 in high ee.

Organocatalyzed C–C Ring Construction: The Bradshaw/Bonjoch Synthesis of (−)-Cermizine B

Organic Synthesis ◽

10.1093/oso/9780190646165.003.0071 ◽

2017 ◽

Author(s):

Douglass F. Taber

Keyword(s):

San Antonio ◽

Bond Formation ◽

Bryn Mawr ◽

Chemical Laboratory ◽

Enantiomerically Pure ◽

University Of Texas ◽

National University ◽

Institute Of Technology ◽

In a continuation of his studies (OHL20141229, OHL20140811) of organocatalyzed 2+2 photocycloaddition, Thorsten Bach of the Technische Universität München assembled (Angew. Chem. Int. Ed. 2014, 53, 7661) 3 by adding 2 to 1. Li-Xin Wang of the Chengdu Institute of Organic Chemistry also used (Org. Lett. 2014, 16, 6436) an organocatalyst to effect the addition of 5 to 4 to give 6. Shuichi Nakamura of the Nagoya Institute of Technology devised (Org. Lett. 2014, 16, 4452) an organocatalyst that mediated the enantioselective opening of the aziridine 7 to 8. Zhi Li of the National University of Singapore cloned (Chem. Commun. 2014, 50, 9729) an enzyme from Acinetobacter sp. RS1 that reduced 9 to 10. Gregory C. Fu of Caltech developed (Angew. Chem. Int. Ed. 2014, 53, 13183) a phosphine catalyst that directed the addition of 12 to 11 to give 13. Armido Studer of the Westfälische Wilhelms-Universität Münster showed (Angew. Chem. Int. Ed. 2014, 53, 9622) that 15 could be added to 14 to give 16 in high ee. Akkattu T. Biju of CSIR-National Chemical Laboratory described (Chem. Commun. 2014, 50, 14539) related results. The photostimulated enantioselective ketone alkylation developed (Chem. Sci. 2014, 5, 2438) by Paolo Melchiorre of ICIQ was powerful enough to enable the alkylation of 17 with 18 to give 19, overcoming the stereoelectronic preference for axial bond formation. David W. Lupton of Monash University established (J. Am. Chem. Soc. 2014, 136, 14397) the organocatalyzed transformation of the dienyl ester 20 to 21. James McNulty of McMaster University added (Angew. Chem. Int. Ed. 2014, 53, 8450) azido acetone 23 to 22 to give 24 in high ee. There are sixteen enantiomerically-pure diastereomers of the product 27. John C.-G. Zhao of the University of Texas at San Antonio showed (Angew. Chem. Int. Ed. 2014, 53, 7619) that with the proper choice of organocatalyst, with or without subsequent epimerization, it was possible to selectively prepare any one of eight of those diastereomers by the addition of 26 to 25. William P. Malachowski of Bryn Mawr College showed (Tetrahedron Lett. 2014, 55, 4616) that 28, readily prepared by a Birch reduction protocol, was converted by heating followed by exposure to catalytic Me3P to the angularly-substituted octalone 29.