Stereodivergent and Protecting-Group-Free Synthesis of the Helicascolide Family: A Rhodium-Catalyzed Atom-Economical Lactonization Strategy.

Natural products of polyketide origin, in particular small-sized lactones often possess a very broad range of impressive biological activities. An efficient way to demonstrate the concise access to six-membered lactones was emphasized as part of a stereodivergent and protecting-group-free synthesis of all three representatives of the helicascolide family. This strategy features an atom-economical and highly diastereoselective rhodium-catalyzed "head-to-tail" lactonization by an intramolecular addition of ω-allenyl-substituted carboxylic acids to terminal allenes, including the selective construction of a new stereocenter in the newly formed core structures. The excellent selectivities with which the helicascolide precursors were obtained are remarkable, thus resulting in an expeditious and highly efficient natural product synthesis.

[1]  B. Breit,et al.  Regioselective Rhodium-Catalyzed Addition of 1,3-Dicarbonyl Compounds to Terminal Alkynes. , 2016, Organic letters.

[2]  B. Breit,et al.  Z-Selective Hydrothiolation of Racemic 1,3-Disubstituted Allenes: An Atom-Economic Rhodium-Catalyzed Dynamic Kinetic Resolution. , 2015, Angewandte Chemie.

[3]  M. Krische,et al.  Iridium-Catalyzed C-C Coupling of a Simple Propargyl Ether with Primary Alcohols: Enantioselective Homoaldol Addition via Redox-Triggered (Z)-Siloxyallylation. , 2015, Journal of the American Chemical Society.

[4]  B. Breit,et al.  Atom-Economical Dimerization Strategy by the Rhodium-Catalyzed Addition of Carboxylic Acids to Allenes: Protecting-Group-Free Synthesis of Clavosolide A and Late-Stage Modification. , 2015, Angewandte Chemie.

[5]  Lijia Wang,et al.  Catalytic Asymmetric Synthesis of 3-Hydroxy-3-trifluoromethyl Benzofuranones via Tandem Friedel-Crafts/Lactonization Reaction. , 2015, Organic letters.

[6]  T. Nishimura,et al.  Iridium-catalyzed asymmetric cyclization of alkenoic acids leading to γ-lactones. , 2015, Chemical communications.

[7]  B. Breit,et al.  Regio- and enantioselective synthesis of N-substituted pyrazoles by rhodium-catalyzed asymmetric addition to allenes. , 2015, Angewandte Chemie.

[8]  G. Somorjai,et al.  Silica-Supported Cationic Gold(I) Complexes as Heterogeneous Catalysts for Regio- and Enantioselective Lactonization Reactions. , 2015, Journal of the American Chemical Society.

[9]  Y. Yeung,et al.  Catalytic and highly enantioselective selenolactonization. , 2015, Organic letters.

[10]  B. Breit,et al.  Asymmetric rhodium-catalyzed addition of thiols to allenes: synthesis of branched allylic thioethers and sulfones. , 2015, Angewandte Chemie.

[11]  B. Breit,et al.  Enantioselective redox-neutral Rh-catalyzed coupling of terminal alkynes with carboxylic acids toward branched allylic esters. , 2015, Journal of the American Chemical Society.

[12]  B. Breit,et al.  Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes. , 2014, Angewandte Chemie.

[13]  E. Carreira,et al.  Discovery of a highly potent anti-inflammatory epoxyisoprostane-derived lactone. , 2014, Journal of the American Chemical Society.

[14]  Jieping Zhu,et al.  Copper-mediated/catalyzed oxyalkylation of alkenes with alkylnitriles. , 2014, Chemistry.

[15]  Y. Rhee,et al.  Pd-catalyzed asymmetric intermolecular hydroalkoxylation of allene: an entry to cyclic acetals with activating group-free and flexible anomeric control. , 2014, Journal of the American Chemical Society.

[16]  James Guevara-Pulido,et al.  One-pot sequential organocatalytic Michael-Tishchenko-lactonization reactions. Synthesis of enantioenriched 4,5,6-trisubstituted δ-lactones. , 2014, The Journal of organic chemistry.

[17]  B. Breit,et al.  Unlocking the N(2)  selectivity of benzotriazoles: regiodivergent and highly selective coupling of benzotriazoles with allenes. , 2014, Angewandte Chemie.

[18]  P. Baran,et al.  Development of a concise synthesis of (+)-ingenol. , 2014, Journal of the American Chemical Society.

[19]  M. Jung,et al.  Total synthesis of (18S)- and (18R)-homolargazole by rhodium-catalyzed hydrocarboxylation. , 2014, Chemistry.

[20]  B. Breit,et al.  Atom-economic, regiodivergent, and stereoselective coupling of imidazole derivatives with terminal allenes. , 2014, Angewandte Chemie.

[21]  I. Paterson,et al.  Total Synthesis of the Antimitotic Marine Macrolide (−)-Leiodermatolide , 2014, Angewandte Chemie.

[22]  J. Yadav,et al.  Concise total synthesis of botryolide B , 2014 .

[23]  B. Breit,et al.  Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to allenes: efficient construction of tertiary and quaternary carbon centers. , 2014, Journal of the American Chemical Society.

[24]  T. Janecki.  Natural lactones and lactams : synthesis, occurrence and biological activity , 2013 .

[25]  P. Baran,et al.  14-Step Synthesis of (+)-Ingenol from (+)-3-Carene , 2013, Science.

[26]  K. S. Shankar,et al.  Concise Total Synthesis of Helicascolides A, B, and C , 2013, Synthesis.

[27]  A. Lumbroso,et al.  Katalytische asymmetrische Synthese von Allylalkoholen und Allylalkohol‐Derivaten und deren Anwendung in der organischen Synthese , 2013 .

[28]  A. Lumbroso,et al.  Catalytic asymmetric synthesis of allylic alcohols and derivatives and their applications in organic synthesis. , 2013, Angewandte Chemie.

[29]  B. Breit,et al.  Enantioselective rhodium-catalyzed synthesis of branched allylic amines by intermolecular hydroamination of terminal allenes. , 2012, Angewandte Chemie.

[30]  P. Krishna,et al.  First stereoselective total synthesis of helicascolides A and C , 2012 .

[31]  Henry S Rzepa,et al.  Silver-catalysed enantioselective addition of O-H and N-H bonds to allenes: a new model for stereoselectivity based on noncovalent interactions. , 2012, Chemistry.

[32]  M. White,et al.  Directed metal (oxo) aliphatic C-H hydroxylations: overriding substrate bias. , 2012, Journal of the American Chemical Society.

[33]  U. Lindequist,et al.  Helicascolide C, a new lactone from an Indonesian marine algicolous strain of Daldinia eschscholzii (Xylariaceae, Ascomycota) , 2012 .

[34]  A. Lumbroso,et al.  Atom economic macrolactonization and lactonization viaredox-neutral rhodium-catalyzed coupling of terminal alkynes with carboxylic acids , 2012 .

[35]  A. Lumbroso,et al.  Enantioselective synthesis of branched allylic esters via rhodium-catalyzed coupling of allenes with carboxylic acids. , 2011, Journal of the American Chemical Society.

[36]  M. White,et al.  Synthetic versatility in C-H oxidation: a rapid approach to differentiated diols and pyrans from simple olefins. , 2011, Journal of the American Chemical Society.

[37]  Ryan A. Mesch,et al.  Iridium-catalysed direct C–C coupling of methanol and allenes , 2011, Nature Chemistry.

[38]  A. Lumbroso,et al.  Redox-neutral atom-economic rhodium-catalyzed coupling of terminal alkynes with carboxylic acids toward branched allylic esters. , 2011, Journal of the American Chemical Society.

[39]  S. Denmark,et al.  Lewis base catalysis of bromo- and iodolactonization, and cycloetherification , 2010, Proceedings of the National Academy of Sciences.

[40]  Guosheng Liu,et al.  Scope and mechanism of allylic C-H amination of terminal alkenes by the palladium/PhI(OPiv)2 catalyst system: insights into the effect of naphthoquinone. , 2010, Journal of the American Chemical Society.

[41]  R. Peters,et al.  Catalytic asymmetric formation of delta-lactones from unsaturated acyl halides. , 2010, Chemistry.

[42]  D. Hall,et al.  Total synthesis of (+)-chinensiolide B via tandem allylboration/lactonization. , 2010, Journal of the American Chemical Society.

[43]  K. K. Hii,et al.  Copper-catalysed intramolecular O-H addition to unactivated alkenes , 2009 .

[44]  Tamio Hayashi,et al.  Rhodium-catalyzed asymmetric hydroalkoxylation and hydrosulfenylation of diphenylphosphinylallenes. , 2009, Chemical communications.

[45]  Brian Samas,et al.  A highly enantioselective allylic amination reaction using a commercially available chiral rhodium catalyst: resolution of racemic allylic carbonates. , 2009, Organic letters.

[46]  M. Sigman,et al.  A general and efficient catalyst system for a Wacker-type oxidation using TBHP as the terminal oxidant: application to classically challenging substrates. , 2009, Journal of the American Chemical Society.

[47]  M. Krische,et al.  Iridium-catalyzed hydrocarboxylation of 1,1-dimethylallene: byproduct-free reverse prenylation of carboxylic acids. , 2008, Organic letters.

[48]  S. Denmark,et al.  Lewis base activation of Lewis acids: development of a Lewis base catalyzed selenolactonization. , 2007, Organic letters.

[49]  G. L. Hamilton,et al.  A Powerful Chiral Counterion Strategy for Asymmetric Transition Metal Catalysis , 2007, Science.

[50]  S. Stahl,et al.  Two-faced reactivity of alkenes: cis- versus trans-aminopalladation in aerobic Pd-catalyzed intramolecular aza-Wacker reactions. , 2007, Journal of the American Chemical Society.

[51]  J. Campagne,et al.  Synthetic Approaches to α,β-Unsaturated δ-Lactones and Lactols , 2007 .

[52]  Z. Huo,et al.  Suppression of β-hydride elimination in the intramolecular hydrocarboxylation of alkynes leading to the formation of lactones , 2007 .

[53]  A. Rimando,et al.  Polyketides: Biosynthesis, Biological Activity, and Genetic Engineering , 2007 .

[54]  E. Duñach,et al.  Novel Catalytic Tandem Isomerisation/Cyclisation Reaction of α‐Methallyloxy Carboxylic Acids , 2006 .

[55]  J. Campagne,et al.  Macrolactonizations in the total synthesis of natural products. , 2006, Chemical reviews.

[56]  Cai-Guang Yang,et al.  Intramolecular additions of alcohols and carboxylic acids to inert olefins catalyzed by silver(I) triflate. , 2005, Organic letters.

[57]  P. Floreancig,et al.  Investigations of the scope and mechanism of the tandem hydroesterification/lactonization reaction. , 2004, Organic letters.

[58]  K. M. Muraleedharan,et al.  Halo- and selenolactonisation: the two major strategies for cyclofunctionalisation , 2004 .

[59]  Yoshinori Yamamoto,et al.  Palladium-catalyzed intramolecular asymmetric hydroamination of alkynes. , 2004, Journal of the American Chemical Society.

[60]  M. White,et al.  A sulfoxide-promoted, catalytic method for the regioselective synthesis of allylic acetates from monosubstituted olefins via C-H oxidation. , 2004, Journal of the American Chemical Society.

[61]  B. Trost,et al.  Asymmetric transition-metal-catalyzed allylic alkylations: applications in total synthesis. , 2003, Chemical reviews.

[62]  Tamio Hayashi,et al.  High enantioselectivity in rhodium-catalyzed allylic alkylation of 1-substituted 2-propenyl acetates. , 2003, Organic letters.

[63]  M. Gruttadauria,et al.  Studies on the stereoselective selenolactonization, hydroxy and methoxy selenenylation of α- and β-hydroxy acids and esters. Synthesis of δ- and γ-lactones , 2003 .

[64]  David K. Leahy,et al.  Regio- and enantiospecific rhodium-catalyzed allylic etherification reactions using copper(I) alkoxides: influence of the copper halide salt on selectivity. , 2002, Journal of the American Chemical Society.

[65]  J. Hsu,et al.  Stereoselective synthesis of delta-lactones from 5-oxoalkanals via one-pot sequential acetalization, Tishchenko reaction, and lactonization by cooperative catalysis of samarium Ion and mercaptan. , 2001, The Journal of organic chemistry.

[66]  J. Staunton,et al.  Polyketide biosynthesis: a millennium review. , 2001, Natural product reports.

[67]  Jürgen Rohr.  Eine neue Rolle für Polyketide , 2000 .

[68]  J. Rohr,et al.  A New Role for Polyketides. , 2000, Angewandte Chemie.

[69]  Y. Fukuyama,et al.  Merrilactone A, a novel neurotrophic sesquiterpene dilactone from Illicium merrillianum , 2000 .

[70]  E. Nandanan,et al.  Palladium-catalyzed reactions of allenes. , 2000, Chemical reviews.

[71]  K. Nicolaou,et al.  STEREOCONTROLLED SYNTHESIS OF THE EVERNINOMICIN A1B(A)C RING FRAMEWORK , 1998 .

[72]  K. Nicolaou,et al.  Stereoselektive Synthese des Everninomicin‐A1B(A)C‐Gerüsts , 1998 .

[73]  W. J. Cole,et al.  A Stereoselective Synthesis of trans-1,2-Disubstituted Alkenes Based on the Condensation of Aldehydes with Metallated 1-Phenyl-1H-tetrazol-5-yl Sulfones , 1998 .

[74]  B. Trost,et al.  Asymmetric Transition Metal-Catalyzed Allylic Alkylations. , 1996, Chemical reviews.

[75]  H. Reichenbach,et al.  Ratjadon: a new antifungal compound from Sorangium cellulosum (myxobacteria) production, physio-chemical and biological properties. , 1995, The Journal of antibiotics.

[76]  Giuseppe Campiani,et al.  A palladium-catalyzed route to huperzine A and its analogues and their anticholinesterase activity , 1993 .

[77]  B. Trost,et al.  Intermolecular Additions and Cycloisomerizations by a Pd‐Catalyzed Sequence of an Intramolecular Redox Reaction and an Addition , 1992 .

[78]  B. Trost,et al.  Intermolekulare Additionen und Cycloisomerisierungen durch eine Pd‐katalysierte Sequenz aus intramolekularer Redoxreaktion und Addition , 1992 .

[79]  T. Oki,et al.  Sultriecin, a new antifungal and antitumor antibiotic from Streptomyces roseiscleroticus. Production, isolation, structure and biological activity. , 1992, The Journal of antibiotics.

[80]  R. Longley,et al.  DISCODERMOLIDE—A NEW, MARINE‐DERIVED IMMUNOSUPPRESSIVE COMPOUND: I. IN VITRO STUDIES , 1991, Transplantation.

[81]  D. Miller,et al.  Improved method for the Wacker oxidation of cyclic and internal olefins , 1990 .

[82]  A. Reitz,et al.  The Wittig olefination reaction and modifications involving phosphoryl-stabilized carbanions. Stereochemistry, mechanism, and selected synthetic aspects , 1989 .

[83]  J. Gloer,et al.  Helicascolides A and B: new lactones from the marine fungus Helicascus kanaloanus. , 1989, Journal of natural products.

[84]  S. Nortey,et al.  Dramatic concentration dependence of stereochemistry in the Wittig reaction. Examination of the lithium salt effect , 1986 .

[85]  J. Tsuji,et al.  Synthetic Applications of the Palladium-Catalyzed Oxidation of Olefins to Ketones , 1984 .

[86]  M. Organ,et al.  Iodolactonization: Synthesis, Stereocontrol, and Compatibility Studies , 2012 .

[87]  Guosheng Liu,et al.  Palladium-catalyzed allylic C-H bond functionalization of olefins. , 2010, Topics in current chemistry.

[88]  Zhan Lu,et al.  Metal-catalyzed enantioselective allylation in asymmetric synthesis. , 2008, Angewandte Chemie.

[89]  Shengming Ma,et al.  Metallkatalysierte enantioselektive Allylierungen in der asymmetrischen Synthese , 2008 .