New synthetic reactions. Convenient approach to methyl 3-oxo-4-pentenoate

Trost, Barry M.; Kunz, Robert A.

doi:10.1021/jo00931a052

Cited by 83 publications

(24 citation statements)

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“…This electrophile had been introduced by Trost in a totally different context 19. Happily, its use resulted in dramatic improvements in selectivity.…”

mentioning

confidence: 99%

A Straightforward Route to Functionalized trans-Diels−Alder Motifs

Lee

Zhang

2010

J. Am. Chem. Soc.

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A sequence consisting of Lewis acid-catalyzed Diels-Alder reaction on a 2-halocyclohexenone, followed by reductive alkylation provides a route to trans-fused octalinones bearing angular methyl groups with functionality corresponding to that which would have been possible from trans-directed Diels-Alder reaction.The concept of prioritized strategic bond disconnection (SBD), so well articulated by the Corey school, is clearly the most powerful resource yet devised in guiding retrosynthetic analysis (RSA)1 en route to complex targets. Recently, we have suggested an approach to RSA which is complementary to the paradigm of strategic bond disconnection. We refer to this mode of retrosynthesis as pattern recognition analysis (PRA).2 Here, the thought exercise focuses on identifying domains within the target. Particularly valuable is the identification of patterns which are accessible by doable chemistry. Indeed, the discernment of patterns around which a synthesis might be organized may well provoke the discovery of new reactions or reaction sequences to enable creation of the molecular architecture inherent in the patterns.One of the pillars of PRA is the notion of building cis-fused ring systems via the DielsAlder (DA) reaction.3 In PRA, the DA cycloaddition is more than a specific reaction type. More broadly, it really implies an overall logic, encompassing a variety of post-DA forays. The DA reaction has been a central implement in the field of chemical synthesis, both in the construction of relatively small molecules as well as for rather complex targets. The scope of PRA in synthetic planning would be much enhanced if the overall logic of the DA reaction could be marshalled to produce trans-fused structures. In principle, the ideal solution to this challenge would be to, somehow, change the stereochemical course of the DA reaction such that the cycloaddition event is antarafacial4 (Figure 1 , 2). While speculations about such a fascinating possibility continue, 5 we have been unable to generate any ideas of value along these lines. The next best approach would be to conduct suprafacial DA reactions, with the important caveat that one of the junction substituents may be replaced by another group with overall inversion of configuration (3→5). In that case, a trans junction would become available from the initial DA-derived cis junction. In intermolecular DA reactions, the junction substituents of the product arise from the dienophile. Hence, this type of exercise would require the use of appropriate dienophiles, carrying substituents amenable to inversion of configuration in the context of a hindered ring junction.6We recently reported instances wherein this line of conjecture could be reduced to practice, though in simplified form.7 The key discovery was that in a cis-decalinoid-like structure (3b), free radical-mediated reduction of a bridgehead C-nitro function can be achieved with inversion of configuration (cf. 3b→5b). While this feasibility demonstration was certainly encouraging, all of the function...

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“…This electrophile had been introduced by Trost in a totally different context 19. Happily, its use resulted in dramatic improvements in selectivity.…”

mentioning

confidence: 99%

A Straightforward Route to Functionalized trans-Diels−Alder Motifs

Lee

Zhang

2010

J. Am. Chem. Soc.

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“…2H,Ha,C(6), H,C (3)), 1.33-1. 18 (m,2H,He@), Ha,C(4)), 1.10-0.97 (m, lH, HaXC (5)), 0.88 (s, 9H, C(CH,),); 13C NMR (100.6 MHz) 144.52 (C(l)), 135.54 (C(l')), 133.53 (C(lO')), 132.35 (C(9')), 128.24 (C(2')), 126.67 (C(4')), 126.60 (C(7')), 125.52 (C(6')), 125.50 (C(5')), 125.29 (C(S')), 125.25 (C(3')), 119.37 (ArCH), 48.23 (C(4)), 37.29 (C(2)), 32.41 (C(CH,),), 29.85 (C(6)), 29.42 (C(3)), 28.66 (C (5) (M+, loo), 221 (14), 193 (13), 180 (24), 179 (57), 178 (261, 167 (21), 166 (18), 165 (62), 154 (30), 153 (161, 152 ( l l ) , 142 (22), 141 (55),57 (60), 55 (lo), 41 (22); TLC R, 0.48 (hexane); [aID_-3.7" (CHCl,, c = 0.57);…”

Section: [Si-( +)-(4-tert-butylcyclohexy1idene)phenylwrethane (3a)mentioning

confidence: 99%

Enantioselective synthesis of alkylidene cyclohexanes by an asymmetric olefination/cross‐coupling sequence

Denmark¹,

Chen²

1995

Heteroatom Chemistry

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“…4182 (7) 5281 (3) 1094 (3) 74 (2) O (11) 5622 (5) 5627 (3) 1297 (3) 103 (2) O (12) 2983 (6) 5811 (3) 548 (3) 122(2) C (2) 2804(5) 34 13(3) 616(3) 6W) C (3) 2054 (6) 2323 (4) 897 (4) 68(2) C (4) 520 (7) 2487 (6) 1125 (5) 97(3) C (5) 673 (6) 3205 (5) 2167 (4) 91(3) C (6) 1511 (5) 4401 (4) 2272 (4) 68(2) C (7) 3402 (4) 4414 (3) 2620(3) 39U) O (7) 4028 (3) 5555 (2) 2988(2) 54U) 4268(4) 361 5(3) 3662(3) 40U) C (9) 6097 (4) 3826 (3) 4139(3) 48U) O (9) 6902(3) 4000(3) 5156(2) 73U) C (10) 6889 (5) 3852 (4) 3271 (3) 6 10) C (11) 5710 (4) 3500 (3) 2087 (3) 54 (2) ' ) See Footnote a in Table 4.…”

Section: C13m)unclassified

Structures of Ring‐Enlargement Products

Aono

Bieri

Hesse

et al. 1985

Helvetica Chimica Acta

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Crystal structures have been determined of methyl trans-1 -hydroxy-6-nitro-3-oxobicyclo[4.4.0]decane-2-carboxylate (19), cis-3-methyl-6-nitro-2-oxabicyclo[4.4.O]decan-1-01 (2), cis-7-hydroxy-1 -nitrobicyclo[5.4.0]undecan%one (13), and the medium-ring compounds 2-acetyl-4-nitrocyclooctanone (9), methyl 5-nitro-2-oxocyclooctanecarboxylate (4), 2-acetyl-4-nitrocyclononanone (ll), 2-acetyl-4-nitrocyclodecanone (15), benzyl 5-nitro-2,1 l-dioxocycloundecanecarboxylate (24), methyl 5-nitro-2,12-dioxocyclododecanecarboxylate (21), and 8-nitro-11 -oxo-13-tridecanolide (7), which are intermediates, side products, or end products of the 'Zip' ring-enlargement reaction. The conformations of most of the medium-ring compounds are very similar to equal-sized ring compounds previously determined by other authors. ~ ~In the past, a new method for ring enlargement by the so-called 'Zip' reaction was developed by which a number of new polyaminolactams were synthesized starting from lactams [ 11. The same reaction principle was followed to convert carbocyclic compounds 2,Part of the thesis of K. K. ') Postdoctoral fellow 1980182.

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New synthetic reactions. Convenient approach to methyl 3-oxo-4-pentenoate

Cited by 83 publications

References 1 publication

A Straightforward Route to Functionalized trans-Diels−Alder Motifs

A Straightforward Route to Functionalized trans-Diels−Alder Motifs

Enantioselective synthesis of alkylidene cyclohexanes by an asymmetric olefination/cross‐coupling sequence

Structures of Ring‐Enlargement Products

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