Iterative Assembly of Chiral Alcohols Utilizing CMMP-Mediated Mitsunobu Reactions

Abstract

An iterative assembly of chiral alcohol building blocks is reported utilizing cyanomethylene trimethylphosphorane (CMMP)-mediated Mitsunobu reactions. 1,3-Benzodithiole tetraoxide (BDT) was used as the platform to prepare long-chain saturated compounds with multiple stereocenters en route to polyisoprenoid natural products. Selectively protected chiral 1,3-butanediols played a key role in iterative chain elongation for the construction of 1,5-dimethyl branched arrays with high stereocontrol.

Key words

Mitsunobu reaction - BDT - chiral alcohols - stereochemistry - polyisoprenoids - CMMP - desulfonylation

Publication History

Received: 13 August 2023

Accepted after revision: 13 September 2023

Accepted Manuscript online:
13 September 2023

Article published online:
26 October 2023

• References

• 1a Mitsunobu O. Synthesis 1981; 1
• 1b But TY. S, Toy PH. Chem. Asian J. 2007; 2: 1340
• 1c Swamy KC. K, Kumar NN. B, Balaraman E, Kumar KV. P. P. Chem. Rev. 2009; 109: 2551
• 1d Fletcher S. Org. Chem. Front. 2015; 2: 739
• 2 Dryzhakov M, Richmond E, Moran J. Synthesis 2016; 48: 935
• 3 Itô S, Tsunoda T. Pure Appl. Chem. 1999; 71: 1053
• 4a Tsunoda T, Ozaki F, Itô S. Tetrahedron Lett. 1994; 35: 5081
• 4b Tsunoda T, Nagaku M, Nagino C, Kawamura Y, Ozaki F, Hioki H, Itô S. Tetrahedron Lett. 1995; 36: 2531
• 5 Tsunoda T, Otsuka J, Yamamiya Y, Itô S. Chem. Lett. 1994; 23: 539
• 6 Tsunoda T, Itô S. J. Synth. Org. Chem. Jpn. 1997; 55: 631
• 7a Tsunoda T, Nagino C, Oguri M, Itô S. Tetrahedron Lett. 1996; 37: 2459
• 7b Tsunoda T, Uemoto K, Ohtani T, Kaku H, Itô S. Tetrahedron Lett. 1999; 40: 7359
• 7c Sakamoto I, Kaku H, Tsunoda T. Chem. Pharm. Bull. 2003; 51: 474
• 7d Hwang J.-T. Cyanomethylenetrimethylphosphorane, Encyclopedia of Reagents for Organic Synthesis. Wiley; DOI: 10.1002/047084289X.rn00315
• 8a Kündig EP, Cunningham AF. Tetrahedron 1988; 44: 6855
• 8b Zhang S, Li J, Zhao S, Wang W. Tetrahedron Lett. 2010; 51: 1766
• 8c Zheng H, Li Z, Jing J, Xue X.-S, Cheng J.-P. Angew. Chem. Int. Ed. 2021; 60: 9401
• 9 Trost BM, Kalnmals CA. Chem. Eur. J. 2019; 25: 11193
• 10a Shing TK. M, Li L, Narkunan K. J. Org. Chem. 1997; 62: 1617
• 10b Takacs JM, Xu Z, Jiang X.-t, Leonov AP, Theriot GC. Org. Lett. 2002; 4: 3843
• 10c Prakash GK. S, Chacko S, Alconcel S, Stewart T, Mathew T, Olah GA. Angew. Chem. Int. Ed. 2007; 46: 4933
• 11 Nájera C, Yus M. Tetrahedron 1999; 55: 10547
• 12a Shiozaki H, Miyahara M, Otsuka K, Miyako K, Honda A, Takasaki Y, Takamizawa S, Tukada H, Ishikawa Y, Sakai R, Oikawa M. Org. Lett. 2018; 20: 3403
• 12b Irie R, Miyahara M, Nakamura S, Honda A, Sakai R, Oikawa M. J. Nat. Prod. 2020; 83: 2769
• 13a Eguchi T, Terachi T, Kakinuma K. J. Chem. Soc., Chem. Commun. 1994; 137
• 13b Li N.-S, Piccirilli JA. Tetrahedron 2013; 69: 9633
• 13c Van Summeren RP, Reijmer SJ. W, Feringa BL, Minnaard AJ. Chem. Commun. 2005; 1387
• 13d Ruiz J, Oger P, Soulére L, Popowycz F. J. Org. Chem. 2021; 86: 9396
• 14a Van Summeren RP, Moody DB, Feringa BL, Minnaard AJ. J. Am. Chem. Soc. 2006; 128: 4546
• 14b Li N.-S, Scharf L, Adams EJ, Piccirilli JA. J. Org. Chem. 2013; 78: 5970
• 14c Andringa RL. H, de Kok NA. W, Driessen AJ. M, Minnaard AJ. Angew. Chem. Int. Ed. 2021; 60: 17497
• 15a Netscher T. Vitam. Horm. 2007; 76: 155
• 15b Eggersdorfer M, Laudert D, Létinois U, McClymont T, Medlock J, Netscher T, Bonrath W. Angew. Chem. Int. Ed. 2012; 51: 12960
• 15c Kundu S, Sarkar D. J. Heterocycl. Chem. 2023; 60: 345
• 16a Burns M, Essafi S, Bame JR, Bull SP, Webster MP, Balieu S, Dale JW, Butts CP, Harvey JN, Aggarwal VK. Nature 2014; 513: 183
• 16b Bootwicha T, Feilner JM, Myers EL, Aggarwal VK. Nat. Chem. 2017; 9: 896
• 17a Breuilles P, Oddon G, Uguen D. Tetrahedron Lett. 1997; 38: 6607
• 17b Krishna PR, Prabhakar S. Tetrahedron Lett. 2013; 54: 3788
• 18a Brown AC, Carpino LA. J. Org. Chem. 1985; 50: 1749
• 18b Huang B.-q, Chen Y, Zhang X.-j, Yan M. Eur. J. Org. Chem. 2021; 3015
• 18c Pan P, Chen L, Zhang X.-j, Yan M. Tetrahedron 2021; 96: 132371
• 19a Hanessian S, Giroux S, Mascitti V. Synthesis 2006; 1057
• 19b ter Horst B, Feringa BL, Minnaard AJ. Chem. Commun. 2010; 46: 2535
• 19c Holzheimer M, Buter J, Minnaard AJ. Chem. Rev. 2021; 121: 9554
• 20 Ghostin J, Bordereau C, Braekman JC. Nat. Prod. Res. 2011; 25: 560
• 21a Landa A, Puente Á, Santos JI, Vera S, Oiarbide M, Palomo C. Chem. Eur. J. 2009; 15: 11954
• 21b Villaescusa L, Hernández I, Azcune L, Rudi A, Mercero JM, Landa A, Oiarbide M, Palomo C. J. Org. Chem. 2023; 88: 972