Intermediates

Claim 2

A process for the synthesis of a polyribonucleotide or polydeoxyribonucleotide comprising (a) contacting a carrier-bound ribonucleotide or deoxyribonucleotide with a ribonucleoside H-phosphonate or deoxyribonucleotide H-phosphonate in the presence of an acylating agent under conditions for condensing the carrier-bound ribonucleotide or deoxyribonucleotide with the ribonucleoside H-phosphonate or deoxyribonucleoside H-phosphonate, wherein a hydroxyl of the ribonucleoside H-phosphonate or deoxynucleoside H-phosphonate is substituted with a blocking group for restricting the condensation reaction to the carrier-bound ribonucleotide or deoxyribonucleotide, (b) removing the blocking group from the ribonucleotide or deoxyribonucleotide hydroxyl, and (c) sequentially repeating steps (a) and (b) until a polynucleotide H-phosphonate having greater than two nucleotides has been obtained.

Claim 3

The method of claim 1 wherein the dehydrating agent is an organic acid halide.

Claim 4

The method of claim 1 wherein the acylating agent is an acid chloride.

Claim 5

The method of claim 1 wherein the step (d) occurs only after the entire polynucleotide H-phosphonate has been synthesized.

Claim 6

The process of claim 1 wherein the carrier is a polymer covalently bonded to the 3'-hydroxyl of the ribonucleotide or deoxyribonucleotide.

Claim 7

The process of claim 5 wherein the carrier is selected form the group consisting of controlled pore glass, silica gel and polystyrene.

Claim 8

The process of claim 1 further comprising contacting the polynucleotide H-phosphonate with an oxidizing agent capable of oxidizing the H-phosphonate moiety.

Claim 9

The process of claim 7 wherein the oxidizing agent is selected from the group consisting of aqueous iodine, N-chlorosuccinimide, N-bromosuccinimide, and a salt of periodic acid.

Claim 10

The process of claim 7 wherein the polynucleotide H-phosphonate is contacted with ROH, wherein R is alkyl, aryl, or heteroaryl containing from 1 to 5 S, N or O atoms and less than 10 carbon atoms, under conditions for producing an internucleotide triester.

Claim 11

The process of claim 9 wherein the heteroaryl group is fluorescent.

Claim 12

The process of claim 7 wherein the polynucleotide H-phosphonate is contacted with S 8 under conditions for producing an internucleotide thiophosphate.

Claim 13

A compound having the formula ##STR17## wherein Y is a positively charged counterion, n is ≧1, M is a ribonucleoside or deoxyribonucleoside, and the ribonucleosides or deoxyrobonucleoside are covalently linked through their 5' and 3' hydroxyl groups.

Claim 14

A compound having the formula ##STR17## wherein Y is a positively charged counterion, n is ≧1, M is a ribonucleoside or deoxyribonucleoside, and the ribonucleosides or deoxyrobonucleoside are covalently linked through their 5' and 3' hydroxyl groups.

Claim 15

The compound of claim 12 wherein M is a blocked nucleoside.

Claim 16

The compound of claim 12 wherein the blocking group is a dialkyl formamidine.

Claim 17

A process for the synthesis of a polyribonucleotide or polydeoxyribonucleotide comprising (a) contacting a carrier-bound ribonucleotide or deoxyribonucleotide with a ribonucleoside H-phosphonate or deoxyribonucleotide H-phosphonate in the presence of an acylating agent under conditions for condensing the carrier-bound ribonucleotide or deoxyribonucleotide with the ribonucleoside H-phosphonate or deoxyribonucleoside H-phosphonate; wherein the acylating agent has the structure ##STR18## wherein A is selected form the group consisting of aryl, heteroaryl, and tertiary alkyl, the tertiary carbon being bonded directly to the carbonyl carbon, and wherein X is halogen or pseudohalogen; and wherein a hydroxyl of the ribonucleoside H-phosphonate or deoxynucleoside H-phosphonate is substituted with a blocking group for restricting the condensation reaction to the carrier-bound ribonucleotide or deoxyribonucleotide, (b) removing the blocking group from the ribonucleotide or deoxyribonucleotide hydroxyl, and (c) sequentially repeating steps (a) and (b) until a polynucleotide H-phosphonate having greater than two nucleotides has been obtained.

Claim 18

A process for the synthesis of a polyribonucleotide or polydeoxyribonucleotide comprising (a) contacting a carrier-bound ribonucleotide or deoxyribonucleotide with a ribonucleoside H-phosphonate or deoxyribonucleotide H-phosphonate in the presence of an acylating agent under conditions for condensing the carrier-bound ribonucleotide or deoxyribonucleotide with the ribonucleoside H-phosphonate or deoxyribonucleoside H-phosphonate; wherein the acylating agent has the structure ##STR18## wherein A is selected form the group consisting of aryl, heteroaryl, and tertiary alkyl, the tertiary carbon being bonded directly to the carbonyl carbon, and wherein X is halogen or pseudohalogen; and wherein a hydroxyl of the ribonucleoside H-phosphonate or deoxynucleoside H-phosphonate is substituted with a blocking group for restricting the condensation reaction to the carrier-bound ribonucleotide or deoxyribonucleotide, (b) removing the blocking group from the ribonucleotide or deoxyribonucleotide hydroxyl, and (c) sequentially repeating steps (a) and (b) until a polynucleotide H-phosphonate having greater than two nucleotides has been obtained.

Claim 19

The method of claim 15 wherein the tertiary alkyl has the structure ##STR19## in which R is the same or different normal or branched selected from the group consisting of alkyl, heteroalkyl, aryl and heteroaryl.

Claim 20

The method of claim 16 wherein X is chloride.

Claim 21

The method of claim 15 wherein the acylating agent is an acyl halide having a tertiary carbon bonded directly to the acyl carbon.

Claim 22

The method of claim 18 wherein the acylating agent is pivaloyl chloride.

Claim 23

The process of claim 15 wherein the carrier is a polymer covalently bonded to the 3'-hydroxyl of the ribonucleotide or deoxyribonucleotide.

Claim 24

The process of claim 20 wherein the carrier is selected from the group consisting of controlled pore glass, silica gel and polystyrene.

Claim 25

The process of claim 15 further comprising contacting the polynucleotide H-phosphonate with an oxidizing agent capable of oxidizing the H-phosphonate moiety.

Claim 26

The process of claim 22 wherein the oxidizing agent is selected from the group consisting of aqueous iodine, N-chlorosuccinimide, N-bromosuccinimide, and a salt of periodic acid.

Claim 27

The process of claim 22 wherein the polynucleotide H-phosphonate is contacted with ROH, wherein R is alkyl, aryl, or heteroaryl containing from 1 to 5 S, N or O atoms and less than 10 carbon atoms, under conditions for producing an internucleotide triester.

Claim 28

The process of claim 24 wherein the heteroaryl group is fluorescent.