Stereoselective Synthesis of the Disaccharide Unit of Incednine

Abbott, Jason R.; Roush, William

doi:10.1021/ol303093z

Cited by 9 publications

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“…Despite the great importance of these compounds in organic chemistry, 61 the number of reported methods for their preparation is limited. 62 − 64 Thiosilanes are usually obtained through the stoichiometric reaction of a chlorosilane and a metal thiolate. Only a few catalytic systems have been developed for this purpose.…”

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“…Extending this process to other coupling partners, complex 4 also has the ability to couple thiols with silanes and boronates, generating the corresponding thioethers. Despite the great importance of these compounds in organic chemistry, the number of reported methods for their preparation is limited. − Thiosilanes are usually obtained through the stoichiometric reaction of a chlorosilane and a metal thiolate. Only a few catalytic systems have been developed for this purpose. , Several thiols and silanes are well tolerated by the dehydrogenative coupling system, achieving high conversion in all cases.…”

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From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story

2014

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ConspectusOne of the most important challenges in catalyst design is the synthesis of stable promoters without compromising their activity. For this reason, it is important to understand the factors leading to decomposition of such catalysts, especially if side-products negatively affect the activity and selectivity of the starting complex. In this context, the understanding of termination and decomposition processes in olefin metathesis is receiving significant attention from the scientific community. For example, the decomposition of ruthenium olefin metathesis precatalysts in alcohol solutions can occur during either the catalyst synthesis or the metathesis process, and such decomposition has been found to be common for Grubbs-type precatalysts. These decomposition products are usually hydridocarbonyl complexes, which are well-known to be active in several transformations such as hydrogenation, terminal alkene isomerization, and C–H activation chemistry. The reactivity of these side products can be unwanted, and it is therefore important to understand how to avoid them and maybe also important to keep an open mind and think of ways to use these in other catalytic reactions.A showcase of these decomposition studies is reported in this Account. These reports analyze the stability of ruthenium phenylindenylidene complexes, highly active olefin metathesis precatalysts, in basic alcohol solutions. Several different decomposition processes can occur under these conditions depending on the starting complex and the alcohol used. These indenylidene-bearing metathesis complexes display a completely different behavior compared with that of other metathesis precatalysts and show an alternative competitive alcoholysis pathway, where rather than forming the expected hydrido carbonyl complexes, the indenylidene fragment is transformed into a η1-indenyl, which then rearranges to its η5-indenyl form. In particular, [RuCl(η5-(3-phenylindenylidene)(PPh3)2] has been found to be extremely active in numerous transformations (at least 20) as well as compatible with a broad range of reaction conditions, rendering it a versatile catalytic tool. It should be stated that the η5-phenyl indenyl ligand shows enhanced catalytic activity over related half-sandwich ruthenium complexes. The analogous half-sandwich (cyclopentadienyl and indenyl) ruthenium complexes show lower activity in transfer hydrogenation and allylic alcohol isomerization reactions. In addition, this catalyst allows access to new phenylindenyl ruthenium complexes, which can be achieved in a very straightforward manner and have been successfully used in catalysis. This Account provides an overview of how mechanistic insights into decomposition and stability of a well-known family of ruthenium metathesis precatalysts has resulted in a series of novel and versatile ruthenium complexes with unexpected reactivity.

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From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story

2014

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Strategies Toward Protection of 1,2‐ and 1,3‐Diols in Carbohydrate Chemistry

Schuler¹,

Tatibouët²

2018

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Improved synthesis of key fragments for the preparation of natural product incednine

et al. 2019

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Stereoselective Synthesis of the Disaccharide Unit of Incednine

Abstract: A stereoselective synthesis of a fully protected version of the disaccharide unit (2) of incednine (1) is described. The synthesis of 2 proceeds in 4.7% overall yield from commercially available allyl α-D-galactopyranoside over the longest linear sequence.

Cited by 9 publications

References 20 publications

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story

Strategies Toward Protection of 1,2‐ and 1,3‐Diols in Carbohydrate Chemistry

Improved synthesis of key fragments for the preparation of natural product incednine

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Stereoselective Synthesis of the Disaccharide Unit of Incednine

Abstract: A stereoselective synthesis of a fully protected version of the disaccharide unit (2) of incednine (1) is described. The synthesis of 2 proceeds in 4.7% overall yield from commercially available allyl α-D-galactopyranoside over the longest linear sequence.

Cited by 9 publications

References 20 publications

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η5-indenyl)(PPh3)2Cl] Story

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η5-indenyl)(PPh3)2Cl] Story

Strategies Toward Protection of 1,2‐ and 1,3‐Diols in Carbohydrate Chemistry

Improved synthesis of key fragments for the preparation of natural product incednine

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Product

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From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story