Alkyne-alcohols => aldehydes

Alkynes Alcohols Aldehydes and Ketones Acids and Derivatives... 

Classify each of the following compounds as an alkane, alkene, alkyne, alcohol, aldehyde, amine, and so forth. 

Scheme 5.1-27 The zinc triflate-catalyzed coupling of alkynes with aldehydes to give propargyl alcohols in an ionic liquid.

Previous syntheses of terminal alkynes from aldehydes employed Wittig methodology with phosphonium ylides and phosphonates. 6 7 The DuPont procedure circumvents the use of phosphorus compounds by using lithiated dichloromethane as the source of the terminal carbon. The intermediate lithioalkyne 4 can be quenched with water to provide the terminal alkyne or with various electrophiles, as in the present case, to yield propargylic alcohols, alkynylsilanes, or internal alkynes. Enantioenriched terminal alkynylcarbinols can also be prepared from allylic alcohols by Sharpless epoxidation and subsequent basic elimination of the derived chloro- or bromomethyl epoxide (eq 5). A related method entails Sharpless asymmetric dihydroxylation of an allylic chloride and base treatment of the acetonide derivative.8 In these approaches the product and starting material contain the same number of carbons. 

Enamines can also be converted to amino alcohols via hydroboration. Allene-boranes react with aldehydes to give alkyne-alcohols. ... 

In 2002, Braga el al. employed a chiral C2-symmetric oxazolidine disulfide as a ligand for the enantioselective synthesis of propargylic alcohols by direct addition of alkynes to aldehydes (Scheme 3.64). Good yields but moderate enantioselectivities (<58% ee) were obtained for the enantioselective alkyny-lation of aldehydes in the presence of ZnEt2. 

Some unusual behaviour was displayed by the benzodisilacyclobutane 84 as described by Ishikawa et al.95 When thermolyzed, it appeared to form the quinodimethane bis-silene species 85 shown in Scheme 13, as confirmed by trapping reactions with f-butyl alcohol, alkynes, or aldehydes, all of which added in a 1,4-manner (see Scheme 13). In the absence of a trapping reagent, 85 decomposed, but not to 86 as claimed earlier.95 ... 

The same authors have also reported the application of green solvents in additions of terminal alkynes to aldehydes in the presence of Zn(OTf)2 and l,8-diazabicyclo[5,4,0]-7-undecene (DBU, Scheme 109).287 The reactions proceeded very slowly, but afforded desirable alcohols 195 in moderate to good yields. 

Carreira and co-workers developed a highly efficient enantioselective addition of terminal alkynes to aldehydes giving propargyl alcohols by the mediation of zinc tri-flate and N-methylephedrine [17]. This reaction serves as a convenient and powerful synthetic route to a wide variety of enantioenriched allenes via propargyl alcohols. Dieter and Yu applied this alkynylation to the asymmetric synthesis of allenes (Scheme 4.12) [18]. Reaction of phenylacetylene with isobutyraldehyde afforded the propargyl alcohol in 80% yield with 99% ee, which was mesylated to 49 in quantitative yield. Reaction of 49 with the cyanocuprate 50 afforded the desired allene 51 with 83% ee. 

Hydrosilylation can be applied to alkenes, alkynes, and aldehydes or ketones. A wide range of metal compounds can be used as a catalyst. The most common and active ones for alkenes and alkynes are undoubtedly based on platinum. Hydrosilylation of C-0 double bonds gives silyl ethers, which are subsequently hydrolysed to their alcohols. The reaction is of interest in its enantioselective version in organic synthesis for making chiral alcohols, as the achiral hydrogenation of aldehydes or ketones does not justify the use of expensive silanes as a reagent. 

CPO catalyzes the oxidation of 2-alkynes to aldehydes in the presence of H202 or tBuOOH via an alcoholic intermediate as depicted in Scheme 2.18 [242]. Propargylic alcohols are rapidly oxidized to the corresponding aldehydes [243] and there is a report about highly enantioselective propargylic hydroxylations catalyzed by CPO [244], In addition, a number of primary alcohols are selectively oxidized to aldehydes in a biphasic mixture of hexane and a buffer (Scheme 2.18) [245, 246]. 

Montgomery and co-workers [36, 42] have shown that organozincs can also couple with alkynes and aldehydes via organonickel intermediates 26 with high degrees of chemo- and stereoselectivities to afford allylic alcohols 27 (Scheme 8.9). Recently, they reported a two-step, four-component synthesis of cyclohexenol de-... 

Anhydrous iron(III) halides catalyse coupling of alkynes and aldehydes.211 Simple terminal alkynes, R CH, react with aldehydes, R2CHO, to give ( ,Z)-1,5-dihalo-1,4-dienes (55). In contrast, non-terminal arylalkynes give ( ,)-o, /3-unsaturated ketones. The catalysts also promote standard Prins cyclization of homoallylic alcohols. Studies of intermediates and of alkyne hydration - together with calculations - all support FeX3 complex formation with alkyne as the activating step. 

Begin to recognize the important functional groups alkene, alkyne, alcohol, ether, aldehyde, ketone, carboxylic acid, ester, amine, nitrile, amide, thiol, and thioether. 

Halides are second only to carboxylic acids in their versatility in organic synthesis. Functional group transformations into alkenes, alkynes, amines, aldehydes, alcohols, ethers, hydrocarbons, ketones and other groups may be performed with ease in high yield. However, the major synthetic importance of halides arises from the ease by which compounds that contain this functionality may be used in carbon-carbon bond-forming reactions and in the preparation of heterocyclic compounds. 

The straightforward addition of 1-alkynes to aldehydes mediated by Gal3 and an amine gives propargylic alcohols in moderate to high yields (Scheme 127).414... 

Oxidation of the vinylborane (using basic hydrogen peroxide) gives a vinyl alcohol (end), resulting from anti-Markovnikov addition of water across the triple bond. This end quickly tautomerizes to its more stable carbonyl (keto) form. In the case of a terminal alkyne, the keto product is an aldehyde. This sequence is an excellent method for converting terminal alkynes to aldehydes. 

Alkenes and alkynes obviously don t fit easily into these categories as they have no bonds to heteroatoms. Aikenes can be made from alcohols by dehydration without any oxidation or reduction so it seems sensible to put them in the alcohol column. Similarly, alkynes and aldehydes are related by hydration/dehydration without oxidation or reduction. 

Another secondary borane useful for the conversion of alkenes into alcohols and of alkynes to aldehydes or ketones is catecholborane (1,3,2-benzodioxaborole), which is prepared from catechol and borane in tetrahydrofuran [1201] (equations 600 and 601). 

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