Heteroatomic coupling carbon-oxygen bonds

Examples of the transition metal catalyzed formation of carbon-heteroatom bonds other than carbon-nitrogen are less abundant. In a recent survey of the copper catalyzed carbon-oxygen bond formation between alcohols and organotrifluroborates the coupling of 3-thienyltrifluoroborate and 2-furfuryl alcohol gave the expected thienyl-furfuryl-ether in good yield (6.83.),113... 

An important point about quaternary carbons requires comment. Until now, we have had no direct correlations for carbons without protons, nor have we been able to see through heteroatoms such as oxygen, nitrogen, sulfur, etc. Both the two- and three-bond coupling correlations of HMBC provide us with both types of critical information. For example, C-4 of caryophyllene oxide at 59.1 ppm has no attached protons, and so far it has only appeared in the l3C spectrum of the compound, and we know that it is quaternary... 

This reaction allows aryl carbon-heteroatom bond formation via an oxidative coupling of arylboronic acids, stannanes or siloxanes with N-H or O-H containing compounds in air. Substrates include phenols, amines, anilines, amides, imides, ureas, carbamates, and sulfonamides. The reaction is induced by a stoichiometric amount of copper(II) or a catalytic amount of copper catalyst which is reoxidized by atmospheric oxygen. 

A characteristic feature of the carbon NMR spectra of dialkyl H-phosphonates is the /(PC) coupling through the oxygen heteroatom. These coupling constants have values in the range 5-8 Hz and can be observed through up to three bonds V(PC) and V(PC) (see A4). 

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