Metal-catalyzed carbon-sulfur bond formation.

The last 15 years of hydroformylation and carbonylation chemistry are reviewed, including technical and commercial aspects.

Progress in hydroformylation and carbonylation

Kunbing Ouyang,†,‡ Wei Hao,† Wen-Xiong Zhang,*,†,§ and Zhenfeng Xi† †Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China ‡Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China

Transition-Metal-Catalyzed Cleavage of C-N Single Bonds.

Organic free radicals have historically been regarded as intermediates poorly suited for selective reactions because of their high reactivity. In the past 25 years it has become apparent that radicals can react in a chemoand regioselective manner. Furthermore, in the past decade, stereoselective transformations of free radicals have been achieved.1 During this time, a variety of useful synthetic strategies have been developed for radical-based C-C bond-forming reactions, and an understanding of the determining parameters for diastereoselective transformations has emerged.1 On the other hand, enantioselective transformations of organic radicals remain uncommon. As recently as 1995, the prevailing view, stated in a review of the field,1a was that “Acyclic diastereocontrol has emerged only recently, but progress has been rapid. Enantioselective reactions of radicals are rare at present, but we believe that their development is now inevitable.” Since this statement was published, inevitability has become reality, and there are now several examples in the literature of enantioselective radical transformations. Early enantioselective radical transformations relied on precedents from successful strategies utilized for other reaction types, as was the case in the development of diastereoselective radical reactions. Thus, chiral auxiliaries used in diastereoselective radical transformations were developed based upon precedents elaborated for enolate alkylations,2 and the enantioselective variants have benefited from strategies used in catalytic DielsAlder3 and other processes. In this Account, we present developments in enantioselective radical transformations that have occurred in the past three years in the context of previous efforts to control configuration in diastereoselective radical reactions. We focus principally on advances made in our own laboratories but mention also important developments from other research groups.

Enantioselective Free Radical Reactions

Transition metal catalysts are formidable tools towards greener chemistry, allowing for low-waste, energy-efficient, and selective reactions. And transition metal-catalysed carbonylation procedures are powerful methodologies for producing carbonyl-containing compounds. The existing reviews/chapters/books are mainly focused on noble metal (Ru, Rh, Ir, Pd, Pt) catalysed carbonylation reactions. In this review, achievements on non-noble metal (Mn, Fe, Cu, Co, Ni) catalysed carbonylative transformations have been summarized and discussed.

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Non-noble metal-catalysed carbonylative transformations

Regiospecific carbonylation and ring expansion of thietanes and oxetanes catalyzed by cobalt and/or ruthenium carbonyls

Sulfur-containing molecules are increasingly crucial in chemistry-related fields and are widely applied in life science, material science, food science, and pharmaceutical science. This perspective focuses on the introduction of green sulfurizing reagents and sustainable sulfurizing methodologies to realize diverse kinds of functionalized transformations and synthetic applications. The text is organized according to the structure of the sulfur-containing molecules and the corresponding synthetic method. It is expected to be of interest to organic chemistry professionals who wish to better understand the insights and applications of organosulfur chemistry transformations. 

Prospects and Challenges in Organosulfur Chemistry

Carbonylation of pyrrolidines, catalyzed by cobalt carbonyl, results in the formation of piperidinones. The reaction is regiospecific in most cases, and the yield of product is increased when ruthenium carbonyl is present as a second catalyst. The dual catalytic system [Co 2 (CO) 8 /Ru 3 (CO) 12 ] is useful for the novel rearrangement of heterocyclic nitrogen ketones ((CH 2 ) n NCH 2 COR, n=4-7] to lactams in 72-93% yields. An unusual metal cataIyzed cyclization reaction of 2,6-dimethylpiperidinyl ketones afforded 5,6,7,8-tetrahydroindolizines in 86-94% yields

Regioselective synthesis of piperidinones by metal-catalyzed ring expansion-carbonylation reactions. Remarkable cobalt and/or ruthenium carbonyl catalyzed rearrangement and cyclization reactions

Divergent sulfur(VI) fluoride exchange linkage of sulfonimidoyl fluorides and alkynes

S ulfur(VI) fluoride cleavage and exchanging linkage, a new generation of linkage chemistry, exhibits enormous potential for combining a range of functional molecules in an increasing number of fields. Herein, we established a metal-free linkage of unactivated alkenes and sulfonimidoyl fluorides via hydrosulfonimidoylation to construct sulfoximines within minute s. An intermolecular hydride transfer process is the key step, and it occurs via overlap of the LUMO in the sulfonimidoyl cation and HOMO in the unactivated alkene, which was confirmed via control experiments with deuterated compounds . DFT calculations further demonstrated the concerted process involving formation of the S-C( sp 3 ) bond and hydride transfer . Remarkably, abundant natural products and pharmaceuticals with multiple heteroatoms and sensitive functional groups have been subjected to the current linkage reaction to achieve various sulfoximine linkages, furnishing the basis for drug discovery and drug conjugation .

Ming De Wang

Papers

Regiospecific carbonylation and ring expansion of thietanes and oxetanes catalyzed by cobalt and/or ruthenium carbonyls

Prospects and Challenges in Organosulfur Chemistry

Regioselective synthesis of piperidinones by metal-catalyzed ring expansion-carbonylation reactions. Remarkable cobalt and/or ruthenium carbonyl catalyzed rearrangement and cyclization reactions

Divergent sulfur(VI) fluoride exchange linkage of sulfonimidoyl fluorides and alkynes

The Linkage of Sulfonimidoyl Fluorides and Unactivated Alkenes via Hydrosulfonimidoylation.