Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones

Golinski, Miroslaw; Brock, Carolyn Pratt; Watt, David S.

doi:10.1021/jo00053a030

Cited by 45 publications

(8 citation statements)

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“…Addition of cyanide can be effected directly with TMSCN in the presence of Zr(KPO 4 ) 2 107 to give 96 or alternatively, if the thioacetal 69 is used, addition of TBSCN with ZnI 2 allows an almost complete diastereoselective attack of the cyanide from the bottom face. 108 Corey-Chaykovsky epoxidation of 1 gives 97, which can be used in ring-expansion reactions. 109 Conjugate addition can be carried out with methylcuprate 110 to furnish 98 with good selectivity for the 1,4-over 1,2-addition product with complete cis control.…”

Section: C-c-bond-forming Reactionsmentioning

confidence: 99%

The Wieland-Miescher Ketone: A Journey from Organocatalysis to Natural Product Synthesis

Bradshaw¹,

Bonjoch²

2011

Synlett

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The Hajos-Parrish-Eder-Sauer-Wiechert reaction can be considered as the origin of asymmetric organocatalysis, giving rise to the Wieland-Miescher ketone 1 (WMK), a versatile building block. Although 40 years have passed since its discovery, a highly enantioselective and scalable synthesis of the WMK has remained elusive. This account details a solution to that problem that came about in the development of methodology towards C-8a WMK analogues as part of the total synthesis of complex diterpene natural products. The work has been placed in the context of the historical background and reactivity of this important building block, highlighting the challenges faced by organocatalysis in large-scale reactions.

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Section: C-c-bond-forming Reactionsmentioning

confidence: 99%

The Wieland-Miescher Ketone: A Journey from Organocatalysis to Natural Product Synthesis

Bradshaw¹,

Bonjoch²

2011

Synlett

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“…The simple addition of an aqueous solution of a cyanide salt to a solution of the substrate in acetic acid represents a simple and relatively safe procedure. 8 In another common method, reaction with trialkylsilyl cyanide reagents may be used to give the O-silylated cyanohydrin derivatives: 9,10 O-TMS cyanohydrins may be hydrolyzed to the free cyanohydrins in acid. Zinc iodide 11 or 18-crown-6 with potassium cyanide 12,13 are commonly used as catalysts for trialkylsilylcyanation: ytterbium tricyanide, 14 Lewis bases, 15 and other Lewis acids 16 have also been used.…”

Section: Racemic Cyanohydrinsmentioning

confidence: 99%

Cyanohydrins in Nature and the Laboratory: Biology, Preparations, and Synthetic Applications

1999

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K., in 1994 with his B.A. degree in Natural Sciences (Chemistry), which included a molecular modeling project with Dr. Jonathan Goodman. He was awarded his Ph.D. degree in 1998 for a thesis on Biocatalytic Preparation and Chemistry of Some Novel Cyanohydrin Systems, under the supervision of Professor Stan Roberts at the Universities of Exeter and Liverpool, U.K. A subsequent Brax Limited Research Fellowship at the University of Liverpool involved the design and synthesis of mass markers as part of a project to investigate the potential of mass spectrometry in genomics and proteomics. He is currently working in the intellectual property area.

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“…However, due to the toxicity and difficulties in handling of HCN, a number of alternative cyanating reagents with less harmful and easily manageable properties have been subsequently introduced 1 2 3 4 . Among other cyanating reagents, TMSCN is one of the most accessed reagents for cyanohydrins synthesis, allowing them to be prepared as cyanohydrin trimethylsilyl ethers 1 2 3 4 7 8 9 10 11 12 13 14 . In this respect, the development of efficient catalysts for the addition of TMSCN to carbonyl compounds has been the focal research point.…”

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confidence: 99%

1-Ethyl-3-methylimidazolium acetate as a highly efficient organocatalyst for cyanosilylation of carbonyl compounds with trimethylsilyl cyanide

Ullah

Chen

Zhang

et al. 2017

Sci Rep

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1-Ethyl-3-methylimidazolium acetate is introduced as a robust organocatalyst for solvent-free cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN). The catalyst loading can be reduced to as low as 0.1–0.0001 mol % under mild reaction conditions, giving considerably high TOF values from 10,843 h−1 to 10,602,410 h−1 in the field of organocatalyzed transformations. The present protocol not only tolerates with extensive carbonyl compounds but also provides somewhat insight into the mechanism of ionic liquids (ILs)-catalyzed reactions.

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Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones

Cited by 45 publications

References 0 publications

The Wieland-Miescher Ketone: A Journey from Organocatalysis to Natural Product Synthesis

The Wieland-Miescher Ketone: A Journey from Organocatalysis to Natural Product Synthesis

Cyanohydrins in Nature and the Laboratory: Biology, Preparations, and Synthetic Applications

1-Ethyl-3-methylimidazolium acetate as a highly efficient organocatalyst for cyanosilylation of carbonyl compounds with trimethylsilyl cyanide

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