Synthesis of bornene-2,2′-diamino-1,1′-binaphthalene conjugates in palladium-catalysed aminocarbonylations

Palladium-catalysed aminocarbonylation of a terpenoic iodoalkene (2-iodo-bornene) model compound with both enantiomerically pure and racemic 2,2′-diamino-1,1′-binaphthalene (BINAM) as the N-nucleophile was carried out. All of the diastereoisomers of the monocarboxamide (N-bornenyl carboxamide) and dicarboxamide (N,N′-dinorbornenylcarboxamide) derivatives were synthesised. The diastereoselectivities of the aminocarbonylation were investigated in both cases: either racemic BINAM was used as the N-nucleophile in the aminocarbonylation of enantiomerically pure 2-iodobornene or racemic iodobornene was aminocarbonylated with enantiomerically pure BINAM with moderate diastereoselectivities. In this way, all possible diastereoisomers of binaphthalene–bornene conjugates were synthesised in moderate to high yields by asymmetric (diastereoselective) aminocarbonylation.

Figure optionsDownload as PowerPoint slide

(R(ax)-(1R,4R)-N-(2′-Amino-[1,1′-binaphthalen]-2-yl)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamide)C31H30N2O[α]D20 = +49.9 (c 1.103, CHCl3)Source of chirality: diastereoselective aminocarbonylation.

(R(ax)-(1R,4R)-1,7,7-Trimethyl-N-(2′-((1R,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamido)-[1,1′-binaphthalen]-2-yl)bicyclo[2.2.1]hept-2-ene-2-carboxamide)C42H44N2O2[α]D20 = −86.3 (c 0.638, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(R(ax)-(1S,4S)-1,7,7-Trimethyl-N-(2′-((1R,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamido)-[1,1′-binaphthalen]-2-yl)bicyclo[2.2.1]hept-2-ene-2-carboxamide)C42H44N2O2[α]D20 = +60.3 (c 1.161, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(R(ax)-(1S,4S)-1,7,7-Trimethyl-N-(2′-((1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamido)-[1,1′-binaphthalen]-2-yl)bicyclo[2.2.1]hept-2-ene-2-carboxamide)C42H44N2O2[α]D20 = +106.8 (c 0.703, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(S(ax)-(1S,4S)-N-(2′-Amino-[1,1′-binaphthalen]-2-yl)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamide)C31H30N2O[α]D20 = +123.2 (c 1.826, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(S(ax)-(1R,4R)-N-(2′-Amino-[1,1′-binaphthalen]-2-yl)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamide)C31H30N2O[α]D20 = −167.1 (c 0.629, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(S(ax)-(1R,4R)-1,7,7-Trimethyl-N-(2′-((1R,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamido)-[1,1′-binaphthalen]-2-yl)bicyclo[2.2.1]hept-2-ene-2-carboxamide)C42H44N2O2[α]D20 = −326.9 (c 0.260, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(S(ax)-(1S,4S)-1,7,7-Trimethyl-N-(2′-((1R,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamido)-[1,1′-binaphthalen]-2-yl)bicyclo[2.2.1]hept-2-ene-2-carboxamide)C42H44N2O2[α]D20 = −52.6 (c 1.161, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(S(ax)-(1S,4S)-1,7,7-Trimethyl-N-(2′-((1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamido)-[1,1′-binaphthalen]-2-yl)bicyclo[2.2.1]hept-2-ene-2-carboxamide)C42H44N2O2[α]D20 = +38.7 (c 0.775, CHCl3)Source of chirality: diastereoselective aminocarbonylation

(S(ax)-(1S,4S)-N-(2′-Amino-[1,1′-binaphthalen]-2-yl)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxamide)C31H30N2O[α]D20 = −33.3 (c 1.352, CHCl3)Source of chirality: diastereoselective aminocarbonylation