Isocyanide-based multicomponent reactions towards cyclic constrained peptidomimetics

• Gijs Koopmanschap,
• Eelco Ruijter and
• Romano V.A. Orru

Beilstein J. Org. Chem. 2014, 10, 544–598, doi:10.3762/bjoc.10.50

• -position and can be obtained for example from β-amino acids. During the Ugi reaction, the tetrazole moiety is obtained from a sigmatropic rearrangement (Scheme 47). Subsequent base-treatment enables β-elimination, which is driven by mesomeric stabilization of the triazole ring, resulting in the desired 5

Synthesis of the B-seco limonoid core scaffold

• Hanna Bruss,
• Hannah Schuster,
• Rémi Martinez,
• Markus Kaiser,
• Andrey P. Antonchick and
• Herbert Waldmann

Beilstein J. Org. Chem. 2014, 10, 194–208, doi:10.3762/bjoc.10.15

• framework of B-seco limonoid natural products by means of a [3,3]-sigmatropic rearrangement are described. Detailed model studies reveal, that an Ireland–Claisen rearrangement can be employed to construct the central C9–C10 bond thereby giving access to the B-seco limonoid scaffold. However, application of

• natural product classes to inspire the synthesis of probes and reagents for chemical biology and medicinal chemistry research, we aimed at the development of a synthetic strategy to get access to the B-seco limonoid scaffold by means of a [3,3]-sigmatropic rearrangement as key step enabling the formation

• alcohol 18 and Mitsunobu reaction installed the required stereochemistry at C14. The free C14 hydroxy group was masked with protecting groups (MOM and TIPS) of different size and chemical nature to examine the face-selectivity of the [3,3]-sigmatropic rearrangement. After selective desilylation, alcohols

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

• Sebastian Krüger and
• Tanja Gaich

Beilstein J. Org. Chem. 2014, 10, 163–193, doi:10.3762/bjoc.10.14

• cyclohepta[cd]oxindole core 32 proved the synthetic versatility of a [3,3]-sigmatropic rearrangement for direct C–C-bond formation at the C4 position of the indole nucleus, and thus provides experimental evidence for the biosynthetic proposal. Applications to natural product synthesis Fatty acid metabolites

An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2013, 9, 2265–2319, doi:10.3762/bjoc.9.265

Sequential Diels–Alder/[3,3]-sigmatropic rearrangement reactions of β-nitrostyrene with 3-methyl-1,3-pentadiene

• Peter A. Wade,
• Alma Pipic,
• Matthias Zeller and
• Panagiota Tsetsakos

Beilstein J. Org. Chem. 2013, 9, 2137–2146, doi:10.3762/bjoc.9.251

• intermediate. The initially isolated nitronic ester cycloadducts underwent tin(IV)-catalyzed interconversion, presumably via zwitterion intermediates. Cycloadducts derived from the reaction at the less substituted double bond of (E)-3-methyl-1,3-pentadiene underwent a [3,3]-sigmatropic rearrangement on heating

• initial assessment of substituent effects on the rearrangement process is presented. Keywords: cycloaddition; diene; nitro; nitronate; rearrangement; Introduction We have previously reported examples of a general new [3,3]-sigmatropic rearrangement, the conversion of O-allyl nitronic esters (nitronates

• )-catalyzed [3,3]-sigmatropic rearrangement of nitronic ester 5 affords nitro compound 16 (vide infra). The rapid interconversion of nitronic esters 2 and 3 likely reflects the greater ease of rotation for the cyclo zwitterion 17. Here bond breaking and reformation is at a secondary rather than tertiary

Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

• Jungho Jun,
• Hyu-Suk Yeom,
• Jun-Hyun An and
• Seunghoon Shin

Beilstein J. Org. Chem. 2013, 9, 1724–1729, doi:10.3762/bjoc.9.198

• polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3

• ]-rearrangement products through the formation of a tight ion–dipole pair. Keywords: gold catalysis; intermolecular coupling; [1,3]-rearrangement; [3,3]-sigmatropic rearrangement; sulfonylacetylene; Introduction Homogeneous gold catalysis has been established during the last decade as a prominent tool in

• undergo intermolecular alkoxylation-[3,3]-sigmatropic rearrangement under Ag(I) or Au(I) catalysis [7][8], allyl ethers that are less nucleophilic due to steric reasons react more slowly and have not been known to undergo similar reactions until recently. In our previous work [9], it was shown that ester

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• such as benzil (61, 1,2-diphenyl-1,2-ethanedione), are treated with two equivalents of a metal acetylide, the bisalcoholate 75 is produced first (Scheme 16) [65]. The expected [3.3]sigmatropic rearrangement of 75 takes place readily (see below, Section 1.4.1) at room temperature (it is, in essence, a

• :3 ratio (Scheme 28) [84]. For the formation of 110 a [2.3]sigmatropic rearrangement of 108 has been suggested, with the intermediately generated propargylallene derivative being stabilized by a prototropic shift to the final product 110. Another route to an unusually functionalized conjugated

Intramolecular carbenoid ylide forming reactions of 2-diazo-3-keto-4-phthalimidocarboxylic esters derived from methionine and cysteine

• Marc Enßle,
• Stefan Buck,
• Roland Werz and
• Gerhard Maas

Beilstein J. Org. Chem. 2012, 8, 433–440, doi:10.3762/bjoc.8.49

• ][6][7][8] illustrate the wide range of applications. As far as sulfonium ylides are concerned, thermally induced isomerisation, that is the 1,2-shift of a substituent (Stevens rearrangement) and [2,3]-sigmatropic rearrangement of allylsulfonium ylides [9][10][11], and the use as C1 building blocks in

• -β-ketoesters 1, stable four- to seven-membered cyclic ylides 2 were obtained (Scheme 1); in the case of R2 = allyl, however, the ylides underwent a spontaneous [2,3]-sigmatropic rearrangement. On the other hand, the conversion of methionine-derived diazoketone 3 into the cyclic sulfonium ylide 4 was

• simultaneous formation of five-ring sulfonium ylide 12c and six-ring carbonyl ylide 14c is immediately followed by intramolecular pericyclic reactions with participation of the allylic π-system. Sulfonium ylide 12c rearranges by the expected [2,3]-sigmatropic rearrangement [3][10][16] to form

Efficient, highly diastereoselective MS 4 Å-promoted one-pot, three-component synthesis of 2,6-disubstituted-4-tosyloxytetrahydropyrans via Prins cyclization

• Naseem Ahmed and
• Naveen Kumar Konduru

Beilstein J. Org. Chem. 2012, 8, 177–185, doi:10.3762/bjoc.8.19

• tetrahydropyrans. After 22 h stirring more side-products than the desired product were observed. This might be due to the formation of an oxo-carbenium intermediate, which further reacted in a [3,3]sigmatropic rearrangement to give another oxo-carbenium ion (Scheme 1). To optimize the reaction yield, we varied the

• conditions (Table 1, entry 9 vs entry 10). The significant improvements in product yields, reaction time and/or diastereoselectivity might be due to the prevention of the [3,3]sigmatropic rearrangement along with the dehydrating activity of MS 4 Å. In addition, we studied the stoichiometric ratio of MS 4 Å

• unsymmetrical tetrahydropyran derivatives in an economical manner. Moreover, it was observed that MS 4 Å might have a vital part in controlling the reversibility of the [3,3]sigmatropic rearrangement. Furthermore, cleavage of the 4-tosyl group under mild conditions afforded 4-hydroxytetrahydropyrans in high

Synthetic applications of gold-catalyzed ring expansions

• David Garayalde and
• Cristina Nevado

Beilstein J. Org. Chem. 2011, 7, 767–780, doi:10.3762/bjoc.7.87

• into the angular triquinane ventricosene in six steps (Scheme 23). 6 Ring expansions involving propargyl acyloxy rearrangements Propargyl carboxylates 80 can be π-activated by gold towards 1,2-acyloxy migration and/or [3,3]-sigmatropic rearrangement. Two different, but mechanistically related

• , intermediates characterize these competitive processes, i.e., 1,2-migration via metal "carbenoid" 81 formation and [3,3]-sigmatropic rearrangement via allenyl acetate 82 as an intermediate (Scheme 24) [5][56][57]. In 2008, Toste and co-workers reported a gold(I)-catalyzed cycloisomerization of cis-pivaloyloxy

Gold catalysis for organic synthesis

• F. Dean Toste

Beilstein J. Org. Chem. 2011, 7, 553–554, doi:10.3762/bjoc.7.63

• from 13 countries underscore the growing importance of homogenous gold catalysis. More importantly, the papers in this Thematic Series highlight the remarkable breath of reactivity that can be accessed using homogenous gold complexes as catalysts; from catalysis of sigmatropic rearrangement

Oxidative allylic rearrangement of cycloalkenols: Formal total synthesis of enantiomerically pure trisporic acid B

• Silke Dubberke,
• Muhammad Abbas and
• Bernhard Westermann

Beilstein J. Org. Chem. 2011, 7, 421–425, doi:10.3762/bjoc.7.54

• steric interference was believed to be a major obstacle of this process, this factor turned out to be unimportant. It is assumed, that the transition state during [3,3]-sigmatropic rearrangement is as shown in Scheme 3 [23][24], where the hydroxyl group is fixed in a pseudo-axial orientation, any other

Application of the diastereoselective photodeconjugation of α,β-unsaturated esters to the synthesis of gymnastatin H

• Ludovic Raffier and
• Olivier Piva

Beilstein J. Org. Chem. 2011, 7, 151–155, doi:10.3762/bjoc.7.21

• from a [1,5]-sigmatropic rearrangement). It was shown that the efficiency of the isomerisation process is highly dependent on the nature of the solvent and on the presence of various additives (e.g., amines) which could catalyse the reketonisation of the transient dienol [4] (Scheme 1). Despite the

Recent advances in carbocupration of α-heterosubstituted alkynes

• Ahmad Basheer and
• Ilan Marek

Beilstein J. Org. Chem. 2010, 6, No. 77, doi:10.3762/bjoc.6.77

• undergoes a subsequent thermal [3,3]-sigmatropic rearrangement to give the corresponding nitrile 27. The presence of the organomagnesium group on 26 is essential for the rearrangement to proceed in good yield (Scheme 12). The silylcupration of N-1-alkynylsulfonylamides 28 led to the desired vinylsilane

• centers. Carbocupration of alkynyl sulfonamide. Tandem carbocupration-sigmatropic rearrangement. Silylcupration of alkynyl sulfonamides. Carbocupration of P-substituted alkynes. Carbocupration of alkynylphosphonates. Carbocupration of thioalkynes. Tandem carbocupration-1,2-metalate rearrangement

A thermally-induced, tandem [3,3]-sigmatropic rearrangement/[2 + 2] cycloaddition approach to carbocyclic spirooxindoles

• Kay M. Brummond and
• Joshua M. Osbourn

Beilstein J. Org. Chem. 2010, 6, No. 33, doi:10.3762/bjoc.6.33

• observed, but are likely intermediates of an infrequently encountered thermal [3,3]-sigmatropic rearrangement of a propargylic acetate. Keywords: allene; propargylic acetate; spirooxindole; thermal [2 + 2] cycloaddition; thermal [3,3]-sigmatropic rearrangement; vinylidene indolin-2-one; Introduction

• 5 could be obtained by way of a thermal [3,3]-sigmatropic rearrangement of the propargylic acetate 6 to give compound 5 where R2 = OAc (Figure 2) [27]. Preparation of propargylic acetate 9a was accomplished by the addition of the lithium acetylide of 8 to N-methyl isatin (7) followed by acetylation

• allenyl acetate in intermediate 11 which in turn arises from the thermal [3,3]-sigmatropic rearrangement of 9a (Figure 3). We have briefly investigated the scope and limitations of this tandem cycloaddition reaction by varying the protecting group on the oxindole nitrogen, altering the substitution on the

Single and double stereoselective fluorination of (E)-allylsilanes

• Marcin Sawicki,
• Angela Kwok,
• Matthew Tredwell and
• Véronique Gouverneur

Beilstein J. Org. Chem. 2007, 3, No. 34, doi:10.1186/1860-5397-3-34

• ] sigmatropic rearrangement. As anticipated and much to our delight, the doubly fluorinated alkene 3 was obtained through a succession of two electrophilic fluorinations. The electrophilic α-fluorination of the ester 4 was performed by treatment with LDA at -78°C followed by addition of N