e.g. Filippa Pettersson or Cancer Res. 75(6) , 1102-12, (2015) or 10.1002/anie.201600521

Total synthesis of (.+-.)-aphidicolin and (.+-.)-. beta.-chamigrene

…, WC Dow, JD Godfrey, S Thaisrivongs

Index: Ireland, Robert E.; Dow, William C.; Godfrey, Jollie D.; Thaisrivongs, Suvit Journal of Organic Chemistry, 1984 , vol. 49, # 6 p. 1001 - 1013

Full Text: HTML

Citation Number: 47

Abstract

Total syntheses of (f)-chamigrene and (*)-aphidicolin are described. Both approaches are based on the spiroannelation of related a-methylene ketones through first hetero-Diels-Alder condensation and then Claisen rearrangement of the derived allyl vinyl ethers. A central feature of the (f)-aphidicolin synthesis is the rearrangement of the intermediate ((trimethylsily1) methyl) cyclobutanone 16 to the aphidicolane bicyclo [3.2. l] octane ring ...

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

~81%

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

~0%

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

N/A Structure

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

~%

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

2,5,5-trimethyl-2,3,4,5,6,7,8,9-octahydrocyclohepta[b]pyran-2-carbaldehyde Structure

2,5,5-trimethyl...

~%

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

2,5,5-Trimethyl-3,4,6,7,8,9-hexahydro-cyclohepta(b)pyran-2-carboxylic Acid, Methyl Ester Structure

2,5,5-Trimethyl...

~%

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

1-tert-butyl-1-cyclohexene Structure

1-tert-butyl-1-...

1,1-dimethyl-2-methylidenecycloheptane Structure

1,1-dimethyl-2-...

1,7,7-trimethylcycloheptene Structure

1,7,7-trimethyl...

5-amino-3-(5-amino-4-cyano-3-methylfuran-2-yl)-3-methyl-2H-furan-4-carbothioamide Structure

5-amino-3-(5-am...

Methyltriphenylphosphonium bromide Structure

Methyltriphenyl...

~%

1,1-dimethyl-2-methylidenecycloheptane Structure

1,1-dimethyl-2-...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

1-tert-butyl-1-cyclohexene Structure

1-tert-butyl-1-...

1,1-dimethyl-2-methylidenecycloheptane Structure

1,1-dimethyl-2-...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

1-tert-butyl-1-cyclohexene Structure

1-tert-butyl-1-...

1,1-dimethyl-2-methylidenecycloheptane Structure

1,1-dimethyl-2-...

1,7,7-trimethylcycloheptene Structure

1,7,7-trimethyl...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

1-tert-butyl-1-cyclohexene Structure

1-tert-butyl-1-...

1,1-dimethyl-2-methylidenecycloheptane Structure

1,1-dimethyl-2-...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

1-tert-butyl-1-cyclohexene Structure

1-tert-butyl-1-...

1,1-dimethyl-2-methylidenecycloheptane Structure

1,1-dimethyl-2-...

1,7,7-trimethylcycloheptene Structure

1,7,7-trimethyl...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

1-tert-butyl-1-cyclohexene Structure

1-tert-butyl-1-...

1,1-dimethyl-2-methylidenecycloheptane Structure

1,1-dimethyl-2-...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

Methyl 3-(dimethylamino)-2-((trimethylsilyl)methyl)propionat Structure

Methyl 3-(dimet...

~78%

methyl 2-(trimethylsilylmethyl)prop-2-enoate Structure

methyl 2-(trime...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

~%

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

2,5,5-Trimethyl-3,4,6,7,8,9-hexahydro-cyclohepta(b)pyran-2-carboxylic Acid, Methyl Ester Structure

2,5,5-Trimethyl...

~%

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

Methyltriphenylphosphonium bromide Structure

Methyltriphenyl...

2,5,5-trimethyl-2,3,4,5,6,7,8,9-octahydrocyclohepta[b]pyran-2-carbaldehyde Structure

2,5,5-trimethyl...

~%

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

isoamyl nitrate Structure

isoamyl nitrate

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

~45%

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

~%

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

~%

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

2,5,5-trimethyl-2,3,4,5,6,7,8,9-octahydrocyclohepta[b]pyran-2-carbaldehyde Structure

2,5,5-trimethyl...

~%

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

2,5,5-Trimethyl-3,4,6,7,8,9-hexahydro-cyclohepta(b)pyran-2-carboxylic Acid, Methyl Ester Structure

2,5,5-Trimethyl...

~%

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

~%

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

~%

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

~%

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

2,5,5-trimethyl-2,3,4,5,6,7,8,9-octahydrocyclohepta[b]pyran-2-carbaldehyde Structure

2,5,5-trimethyl...

~%

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

2,5,5-Trimethyl-3,4,6,7,8,9-hexahydro-cyclohepta(b)pyran-2-carboxylic Acid, Methyl Ester Structure

2,5,5-Trimethyl...

~%

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

~%

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

2,5,5-trimethyl-2,3,4,5,6,7,8,9-octahydrocyclohepta[b]pyran-2-carbaldehyde Structure

2,5,5-trimethyl...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

2,5,5-Trimethyl-3,4,6,7,8,9-hexahydro-cyclohepta(b)pyran-2-carboxylic Acid, Methyl Ester Structure

2,5,5-Trimethyl...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

~%

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

methyl 5,5,9-trimethylspiro[5.5]undec-9-ene-1-carboxylate Structure

methyl 5,5,9-tr...

~93%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

1,2,2-trimethylcycloheptanol Structure

1,2,2-trimethyl...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

3,3-dimethyl-2-methylidenecycloheptan-1-one Structure

3,3-dimethyl-2-...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

2-ethenyl-2,5,5-trimethyl-3,4,6,7,8,9-hexahydrocyclohepta[b]pyran Structure

2-ethenyl-2,5,5...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

2,5,5-trimethyl-2,3,4,5,6,7,8,9-octahydrocyclohepta[b]pyran-2-carbaldehyde Structure

2,5,5-trimethyl...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

2,5,5-Trimethyl-3,4,6,7,8,9-hexahydro-cyclohepta(b)pyran-2-carboxylic Acid, Methyl Ester Structure

2,5,5-Trimethyl...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

3,12,12-trimeth...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

8-hydroxyimino-3,12,12-trimethylspiro[5.6]dodec-3-en-7-one Structure

8-hydroxyimino-...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...

8-diazonio-3,12,12-trimethylspiro[5.6]dodeca-3,7-dien-7-olate Structure

8-diazonio-3,12...

~%

(5,5,9-trimethylspiro[5.5]undec-9-en-1-yl)methanol Structure

(5,5,9-trimethy...