The stereochemistry of organometallic compounds. XXII. The stereochemistry of metal-catalysed hydrogen cyanide addition to olefins

1982 ◽  
Vol 35 (10) ◽  
pp. 2053 ◽  
Author(s):  
WR Jackson ◽  
CG Lovel
Keyword(s):  
Zinc Chloride ◽  
Hydrogen Cyanide ◽  
Isotopic Exchange ◽  
Organometallic Compounds ◽  
Catalyst System

Reactions of (E)-3,3-dimethyl(1,2-D2)but-1-ene with hydrogen cyanide and of (E)-3,3-dimethyl-(1-D)but-1-ene with deuterium cyanide have been shown to proceed in a completely stereospecific cis fashion when a catalyst system based on Pd(diop)2 was used. Reaction between 4-t-butylcyclo-hexene and deuterium cyanide with the catalyst system gave only the equatorial nitriles trans- 4-t-butylcyclohexane-1-carbonitrile and cis-3-t-butylcyclohexane-1-carbonitrile with cis incorporation of deuterium. Use of a catalyst system based on Ni[P(OPh)3]4 and zinc chloride led to significant amounts of isotopic exchange and rearrangement. These results are compared with those from hydroformylation of the olefins, and the mechanism of hydrocyanation is discussed.

scholarly journals Origin of Life’s Building Blocks in Carbon- and Nitrogen-Rich Surface Hydrothermal Vents

Life ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 12 ◽  
Author(s):  
Paul Rimmer ◽  
Oliver Shorttle
Keyword(s):  
Hydrogen Cyanide ◽  
Hydrothermal Vents ◽  
Prebiotic Chemistry ◽  
Organometallic Compounds ◽  
Building Blocks ◽  
Hydrothermal Systems ◽  
Subsurface Water ◽  
Geochemical Environment ◽  
Carbon And Nitrogen ◽  
Submarine Hydrothermal Systems

There are two dominant and contrasting classes of origin of life scenarios: those predicting that life emerged in submarine hydrothermal systems, where chemical disequilibrium can provide an energy source for nascent life; and those predicting that life emerged within subaerial environments, where UV catalysis of reactions may occur to form the building blocks of life. Here, we describe a prebiotically plausible environment that draws on the strengths of both scenarios: surface hydrothermal vents. We show how key feedstock molecules for prebiotic chemistry can be produced in abundance in shallow and surficial hydrothermal systems. We calculate the chemistry of volcanic gases feeding these vents over a range of pressures and basalt C/N/O contents. If ultra-reducing carbon-rich nitrogen-rich gases interact with subsurface water at a volcanic vent they result in 10 − 3 – 1 M concentrations of diacetylene (C4H2), acetylene (C2H2), cyanoacetylene (HC3N), hydrogen cyanide (HCN), bisulfite (likely in the form of salts containing HSO3−), hydrogen sulfide (HS−) and soluble iron in vent water. One key feedstock molecule, cyanamide (CH2N2), is not formed in significant quantities within this scenario, suggesting that it may need to be delivered exogenously, or formed from hydrogen cyanide either via organometallic compounds, or by some as yet-unknown chemical synthesis. Given the likely ubiquity of surface hydrothermal vents on young, hot, terrestrial planets, these results identify a prebiotically plausible local geochemical environment, which is also amenable to future lab-based simulation.

scholarly journals The Transformation by Catalysis of Prebiotic Chemical Systems to Useful Biochemicals: A Perspective Based on IR Spectroscopy of the Primary Chemicals II. Catalysis and the Building of RNA

2020 ◽  
Vol 10 (14) ◽  
pp. 4712
Author(s):  
Ragnar Larsson ◽  
Abdul Malek ◽  
Ingemar Odenbrand
Keyword(s):  
Amino Acids ◽  
Energy Transfer ◽  
Ir Spectroscopy ◽  
Hydrogen Cyanide ◽  
Ribonucleic Acid ◽  
Carbonyl Sulfide ◽  
Catalyst System ◽  
Chemical Systems ◽  
Prebiotic Chemical

Having found that carbonyl sulfide (COS), works well as a catalyst in the transformation of amino acids to polypeptides, we have now tested COS as a catalyst also for the formation of substances that might be thought of as partners in the building of RNA. The model used was selective energy transfer (SET). This model implies that a certain number of vibrational quanta are donated from the catalyst system and a corresponding number of quanta of the reactant accept the energy thus transferred. In this way, we found that carbonyl sulfide, COS, was a perfect catalyst for combining, first, five molecules of formaldehyde to form one molecule of ribose, and next, five molecules of hydrogen cyanide, HCN, to form one molecule of adenine, one of the nucleobases of RNA. However, beyond this, we found that COS was a perfect catalyst for precisely all reactions, needed to build the RNA, ribonucleic acid.

The Stereochemistry of Organometallic Compounds. XXVIII. The Nickel-Catalyzed Addition of Hydrogen Cyanide to Aliphatic Dienes

1987 ◽  
Vol 40 (6) ◽  
pp. 1053 ◽  
Author(s):  
EM Campi ◽  
PS Elmes ◽  
WR Jackson ◽  
CG Lovel ◽  
MKS Probert
Keyword(s):  
Hydrogen Cyanide ◽  
Organometallic Compounds ◽  
Mechanism Of Reaction ◽  
Wide Range ◽  
High Yields ◽  
Very High

Reaction of hydrogen cyanide with a wide range of aliphatic dienes in the presence of nickel(0) catalysts leads to rearrangement of the diene and formation of β,γ -unsaturated nitriles in moderate to very high yields. The mechanism of reaction is discussed in terms of π-allyl-nickel intermediates.

The stereochemistry of organometallic compounds. XXIV. Nickel(0)-catalysed additions of hydrogen cyanide to alkynes

1983 ◽  
Vol 36 (10) ◽  
pp. 1975 ◽  
Author(s):  
WR Jackson ◽  
CG Lovel
Keyword(s):  
Hydrogen Cyanide ◽  
Organometallic Compounds ◽  
Triphenyl Phosphite ◽  
Wide Range

Hydrogen cyanide will add to alkynes bearing a wide range of substituents with cis stereospecificity, high regioselectivity, and in moderate-to-good yields, when the reaction is catalysed by tetrakis- (triphenyl phosphite)nickel(0).

The Stereochemistry of Organometallic Compounds. XXXI. Hydrocyanation of Alkynols

1988 ◽  
Vol 41 (7) ◽  
pp. 1099 ◽  
Author(s):  
WR Jackson ◽  
CG Lovel ◽  
P Perlmutter ◽  
AJ Smallridge
Keyword(s):  
Organometallic Compounds ◽  
Catalyst System ◽  
Steric Effects ◽  
Triphenyl Phosphite ◽  
Catalyst Systems

The regioselectivity of hydrocyanation of a range of alkynols using nickel-based catalyst systems involving either triphenyl phosphite or α,α′-bis(diphenylphosphino)-o-xylene (phmep) has been investigated. The regioselectivity of the hydrocyanations involving the phosphine catalyst reflected dominant steric effects whereas results from the phosphite catalyst system showed some evidence for chelation control. Yields of nitriles from reactions based on the phosphite system were variable, whereas moderate to good yields of distilled products could be obtained consistently by using the phosphine -based system. An explanation for this variation in yield is proposed.

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