(Phenylsulfonyl)allenes as Substrates for Cycloaddition Reactions: Intramolecular Cyclizations onto Unactivated Alkenes

Padwa, Albert; Meske, Michael; Murphree, S. Shaun; Watterson, Scott H.; Ni, Zhi‐Jie

doi:10.1021/ja00132a005

Cited by 74 publications

(28 citation statements)

References 2 publications

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“…Oppolzer contributed to the field of protoilludanes with the synthesis of 6-protoilludene (36), published in 1985. [27] The key step in this short and highly efficient route is an intramolecular type-I magnesium ene-reaction [28,29] followed by an intramolecular [2+2] cycloaddition of a ketene intermediate.…”

Section: -Protoilludene Oppolzer 1985mentioning

confidence: 99%

“…[35] Originally, Stenstrom had intended to construct the protoilludene skeleton through a thermally induced cycloaddition reaction between a phenylsulfonyl-substituted allene and an alkene as demonstrated by Padwa and co-workers. [36] This protocol, however, delivered a 4/5/5-ring system instead of the desired 4/6/5-protoilludene skeleton, so the approach was abandoned and the preparation of an intermediate utilized by Takeshita [19,20] in the synthesis of 7-protoilludene was chosen instead. The key step in Stenstrom's synthesis (Scheme 10) is a ring-closing metathesis (RCM) reaction to elaborate the six-membered ring present in the protoilludene system.…”

Section: -Protoilludene Stenstrom 2003mentioning

confidence: 99%

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Synthesis of Protoilludanes and Related Sesquiterpenes

2011

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Natural products continue to hold the interest and attention of a wide chemical community. This is due to their biological properties and potential applicability in health care and plant protection, as well as their frequently complex molecular architectures and arrays of functionality, which make them a challenge for total synthesis and a testing ground for novel methodology. These criteria are met to an extraordinary degree by protoilludanes, which are sesquiterpenes with a characteristic tricyclic 5/6/4‐framework. The fortieth anniversary of the first protoilludane synthesis has now been taken as an occasion to review the main aspects of this fascinating class of compounds. Biosynthesis, biological properties and the unusually rich variety of synthetic approaches developed over the past forty years are discussed. About 80 different substitution patterns and 15 completed or uncompleted synthetic routes are listed in this review with the goal of providing a multifacetted picture of the changes in and development of synthetic philosophy and methodology from past to present.

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Section: -Protoilludene Oppolzer 1985mentioning

confidence: 99%

Section: -Protoilludene Stenstrom 2003mentioning

confidence: 99%

Synthesis of Protoilludanes and Related Sesquiterpenes

2011

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“…Removal of the silyl protecting group in 18 with tetrabutylammonium fluoride in THF gave the alcohol 19 in 86% yield. 21 The alcohol 19 was reacted with trimethylsilanylpropionic acid in the presence of EDCI (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride) to give the ester 20 in 84% yield.…”

Section: Scheme 6 the Close Proximity Of The Alkyne Functionality Inmentioning

confidence: 99%

A New Route to Highly Functionalized Heterocyclic Rings

et al. 2007

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“…19,22 On the other hand, there are only limited examples of the intramolecular [2 þ 2] cycloaddition reaction of the distal allenic double bond that have produced distal adduct by using a special class of allenes. [23][24][25][26][27][28] Recently, Ma and Gu have synthesized a new eight-membered cyclic compound from 2-(2-methylallyl)-3-(3-methylbuta-1,2-dienyl)cyclohex-2-enone through intramolecular [2 þ 2] cycloaddition and 8-electrocyclization reactions without any catalysts (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

A computational investigation on the sequential rearrangement mechanism of 2‐allyl‐2,4,5‐hexatrienaldehyde involving [1,5]‐hydrogen migration and 8π‐electrocyclization

Zhu¹,

Guo²,

Zhang³

et al. 2007

J Comput Chem

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The sequential rearrangement reaction mechanism of the 2-allyl-2,4,5-hexatrienaldehyde has been studied at the unrestricted Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional (UB3LYP)/6-31G**, Complete Active Space Self-Consistent Field (CAS (8,8))/6-31G**, Configuration Interaction with Single and Double Excitations (CISD)//UB3LYP/6-31G** and the second-order perturbation theory based on the CASSCF reference wave function (CASPT2)//CAS(8,8)/6-31G** levels. Two pathways have been found to be involved for this reaction. The first pathway includes four processes of the rotation of the C3--C4 single bond, the stepwise [2 + 2] cycloaddition, the [1,5]-hydrogen migration, and the ring opening isomerization, while the second pathway undergoes only two processes of the [1,5]-hydrogen migration and the 8pi-electrocyclization. The calculation results indicate that the second pathway is favorable, in good agreement with the recent experimental observation. The whole reaction is stepwise and strong exothermic.

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(Phenylsulfonyl)allenes as Substrates for Cycloaddition Reactions: Intramolecular Cyclizations onto Unactivated Alkenes

Cited by 74 publications

References 2 publications

Synthesis of Protoilludanes and Related Sesquiterpenes

Synthesis of Protoilludanes and Related Sesquiterpenes

A New Route to Highly Functionalized Heterocyclic Rings

A computational investigation on the sequential rearrangement mechanism of 2‐allyl‐2,4,5‐hexatrienaldehyde involving [1,5]‐hydrogen migration and 8π‐electrocyclization

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