Carbanions and Electrophilic Aliphatic Substitution

Chapter 7 Carbanions and Electrophilic Aliphatic Substitution M. L. Birsa, M. L. Birsa Faculty of Chemistry, "Al. I. Cuza" University of Iasi, Iasi, RomaniaSearch for more papers by this author M. L. Birsa, M. L. Birsa Faculty of Chemistry, "Al. I. Cuza" University of Iasi, Iasi, RomaniaSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch7Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary Structure, reactivity, and synthetic applications of sodium diisopropylamide in enolization and orthometallation reactions are reviewed. The transfer of the electrophilic fragment from cumene hydroperoxide to the Zr(IV)-bound enolate has been accompanied by a heterolytic O—O bond cleavage. The formation of a hydrogen bond between the amine hydrogen atom(s) of the salen ligand and the hydroxy group of cumene hydroperoxide played a significant role in stabilizing the stereocontrolled transition state and improving the enantioselectivity. C-Alkylation of potassium enolates with styrenes (CAKES) is one of the highlighted reactions. Base-catalyzed amide CAKES have been studied using a synergistic approach of computation and experimental kinetic studies. The Schlenk equilibrium for thiophene Grignard reagents has been studied using quantum chemical reaction discovery tools. A detailed surface reaction mechanism of zinc-promoted silylation of phenylacetylene and chlorosilane has been reported based on combined experimental characterizations and periodic DFT calculations. References Woltornist , R. A. , Ma , Y. , Algera , R. F. , Zhou , Y. H. , Zhang , Z. R. , and Collum , D. B. , Synthesis-Stuttgart , 52 , 1478 ( 2020 ). 10.1055/s-0039-1690846 CASPubMedWeb of Science®Google Scholar Mao , S. N. , Chen , K. J. , Yan , G. B. , and Huang , D. Y. , Eur. J. Org. Chem. , 525 ( 2020 ). 10.1002/ejoc.201901605 Web of Science®Google Scholar Hao , Y. J. , Hu , X. S. , Zhou , Y. , Zhou , J. , and Yu , J. S. , ACS Catal. , 10 , 955 ( 2020 ). 10.1021/acscatal.9b04480 CASWeb of Science®Google Scholar Mandigma , M. J. P. , Domanski , M. , and Barham , J. P. , Org. Biomol. Chem. , 18 , 7697 ( 2020 ). 10.1039/D0OB01180K CASPubMedWeb of Science®Google Scholar Barham , J. P. , Fouquet , T. N. J. , and Norikane , Y. , Org. Biomol. Chem. , 18 , 2063 ( 2020 ). 10.1039/C9OB02495F CASPubMedWeb of Science®Google Scholar Liu , F. R. , Zhu , L. , Zhang , T. , Zhong , K. B. , Xiong , Q. , Shen , B. M. , Liu , S. H. , Lan , Y. , and Bai , R. P. , ACS Catal. , 10 , 1256 ( 2020 ). 10.1021/acscatal.9b02040 CASWeb of Science®Google Scholar Chen , J. , Gu , H. Y. , Zhu , X. Y. , Nam , W. , and Wang , B. , Adv. Synth. Catal. , 362 , 2976 ( 2020 ). 10.1002/adsc.202000290 CASWeb of Science®Google Scholar Lozovskiy , S. V. and Vasilyev , A. V. , Adv. Synth. Catal. , 362 , 3121 ( 2020 ). 10.1002/adsc.202000534 CASWeb of Science®Google Scholar Curtis , E. R. , Hannigan , M. D. , Vitek , A. K. , and Zimmerman , P. M. , J. Phys. Chem. A , 124 , 1480 ( 2020 ). 10.1021/acs.jpca.9b09985 CASPubMedWeb of Science®Google Scholar Lauridsen , J. M. V. , Cho , S. Y. , Bae , H. Y. , and Lee , J. W. , Organometallics , 39 , 1652 ( 2020 ). 10.1021/acs.organomet.9b00838 Web of Science®Google Scholar Lim , S. , Cho , H. , Jeong , J. , Jang , M. , Kim , H. , Cho , S. H. , and Lee , E. , Org. Lett. , 22 , 7387 ( 2020 ). 10.1021/acs.orglett.0c02752 CASPubMedWeb of Science®Google Scholar Wang , W. F. , Lu , K. , Qin , Y. , Yao , W. W. , Yuan , D. D. , Pullarkat , S. A. , Xu , L. , and Ma , M. T. , Tetrahedron , 76 , 131145 ( 2020 ). 10.1016/j.tet.2020.131145 CASWeb of Science®Google Scholar Huang , P. , Liu , Z. , Shao , Y. Q. , Deng , S. F. , and Liu , B. P. , Phys. Chem. Chem. Phys. , 22 , 22935 ( 2020 ). 10.1039/D0CP04127K CASPubMedWeb of Science®Google Scholar Hartmann , P. E. , Lazzarotto , M. , Pletz , J. , Tanda , S. , Neu , P. , Goessler , W. , Kroutil , W. , Boese , A. D. , and Fuchs , M. , J. Org. Chem. , 85 , 9672 ( 2020 ). 10.1021/acs.joc.0c00992 CASPubMedWeb of Science®Google Scholar Nouch , R. , Woodward , S. , Willcox , D. , Robinson , D. , and Lewis , W. , Organometallics , 39 , 834 ( 2020 ). 10.1021/acs.organomet.0c00005 CASWeb of Science®Google Scholar Zeng , X. M. , Synlett , 31 , 205 ( 2020 ). 10.1055/s-0039-1690764 CASWeb of Science®Google Scholar Konik , Y. A. and Kananovich , D. G. , Tetrahedron Lett. , 61 , 152036 ( 2020 ). 10.1016/j.tetlet.2020.152036 Google Scholar Zambron , B. K. , Synthesis-Stuttgart , 52 , 1147 ( 2020 ). 10.1055/s-0039-1690817 CASWeb of Science®Google Scholar Greene , M. A. , Liu , Y. D. , Sanzone , J. R. , and Woerpel , K. A. , Org. Lett. , 22 , 7518 ( 2020 ). 10.1021/acs.orglett.0c02711 CASPubMedWeb of Science®Google Scholar Zhang , Y. X. , Chen , Y. R. , Zhang , Z. G. , Liu , S. S. , and Shen , X. , Org. Lett. , 22 , 970 ( 2020 ). 10.1021/acs.orglett.9b04505 CASPubMedWeb of Science®Google Scholar Auth , T. , Koszinowski , K. , and O'Hair , R. A. J. , Organometallics , 39 , 25 ( 2020 ). 10.1021/acs.organomet.9b00521 CASWeb of Science®Google Scholar Vijayan , A. , Rao , D. N. , Radhakrishnan , K. V. , Lam , P. Y. S. , and Das , P. , Synthesis-Stuttgart , 53 , 805 ( 2021 ). 10.1055/s-0040-1705971 CASWeb of Science®Google Scholar Pineschi , M. , Eur. J. Org. Chem. , 2643 ( 2020 ). 10.1002/ejoc.201901853 Web of Science®Google Scholar Obst , M. F. , Gevorgyan , A. , Bayer , A. , and Hopmann , K. H. , Organometallics , 39 , 1545 ( 2020 ). 10.1021/acs.organomet.9b00710 CASWeb of Science®Google Scholar Daley , R. A. and Topczewski , J. J. , Synthesis-Stuttgart , 52 , 365 ( 2020 ). 10.1055/s-0039-1690769 CASWeb of Science®Google Scholar Becica , J. and Leitch , D. C. , Synlett , 32 , 641 ( 2021 ). 10.1055/a-1306-3228 CASWeb of Science®Google Scholar Orlandi , M. and Licini , G. , J. Org. Chem. , 85 , 11511 ( 2020 ). 10.1021/acs.joc.0c01768 CASPubMedWeb of Science®Google Scholar Tcyrulnikov , S. and Kozlowski , M. C. , J. Org. Chem. , 85 , 3465 ( 2020 ). 10.1021/acs.joc.9b03203 CASPubMedWeb of Science®Google Scholar Guo , T. , Ding , Y. L. , Zhou , L. L. , Xu , H. Y. , Loh , T. P. , and Wu , X. J. , ACS Catal. , 10 , 7262 ( 2020 ). 10.1021/acscatal.0c02414 CASWeb of Science®Google Scholar Zhao , B. , Shang , R. , Wang , G. Z. , Wang , S. H. , Chen , H. , and Fu , Y. , ACS Catal. , 10 , 1334 ( 2020 ). 10.1021/acscatal.9b04699 CASWeb of Science®Google Scholar Chen , Q. W. , Wu , S. F. , Yan , S. Q. , Li , C. X. , Abduhulam , H. , Shi , Y. H. , Dang , Y. F. , and Cao , C. S. , ACS Catal. , 10 , 8168 ( 2020 ). 10.1021/acscatal.0c01462 CASWeb of Science®Google Scholar Patel , P. and Rousseaux , S. A. L. , Synlett , 31 , 492 ( 2020 ). 10.1055/s-0039-1690718 CASWeb of Science®Google Scholar Lucas , E. L. , Hewitt , K. A. , Chen , P. P. , Castro , A. J. , Hong , X. , and Jarvo , E. R. , J. Org. Chem. , 85 , 1775 ( 2020 ). 10.1021/acs.joc.9b02603 CASPubMedWeb of Science®Google Scholar Chen , W. K. , Li , J. , Xie , H. , and Wang , J. , Org. Lett. , 22 , 3586 ( 2020 ). 10.1021/acs.orglett.0c01052 CASPubMedWeb of Science®Google Scholar Hang , W. , Yi , Y. P. , and Xi , C. J. , Adv. Synth. Catal. , 362 , 2337 ( 2020 ). 10.1002/adsc.202000301 CASWeb of Science®Google Scholar Agata , R. , Lu , S. M. , Matsuda , H. , Isozaki , K. , and Nakamura , M. , Org. Biomol. Chem. , 18 , 3022 ( 2020 ). 10.1039/D0OB00357C CASPubMedWeb of Science®Google Scholar Delaude , L. , Adv. Synth. Catal. , 362 , 3259 ( 2020 ). 10.1002/adsc.202000639 CASWeb of Science®Google Scholar Budagumpi , S. , Keri , R. S. , Achar , G. , and Brinda , K. N. , Adv. Synth. Catal. , 362 , 970 ( 2020 ). 10.1002/adsc.201900859 CASWeb of Science®Google Scholar Das , K. K. , Paul , S. , and Panda , S. , Org. Biomol. Chem. , 18 , 8939 ( 2020 ). 10.1039/D0OB01721C CASPubMedWeb of Science®Google Scholar Zhang , Z. , Ye , J. H. , Ju , T. , Liao , L. L. , Huang , H. , Gui , Y. Y. , Zhou , W. J. , and Yu , D. G. , ACS Catal. , 10 , 10871 ( 2020 ). 10.1021/acscatal.0c03127 CASWeb of Science®Google Scholar Moon , P. J. and Lundgren , R. J. , ACS Catal. , 10 , 1742 ( 2020 ). 10.1021/acscatal.9b04956 CASWeb of Science®Google Scholar Oller , J. , Saez , D. A. , and Vohringer-Martinez , E. , J. Phys. Chem. A , 124 , 849 ( 2020 ). 10.1021/acs.jpca.9b07012 CASPubMedWeb of Science®Google Scholar Li , F. Y. , Zhang , J. Z. , and Xia , F. , J. Phys. Chem. A , 124 , 2029 ( 2020 ). 10.1021/acs.jpca.9b11991 CASPubMedGoogle Scholar Sun , Z. C. and Cundari , T. R. , Phys. Chem. Chem. Phys. , 22 , 24320 ( 2020 ). 10.1039/D0CP04080K CASPubMedWeb of Science®Google Scholar Khedkar , A. and Roemelt , M. , Phys. Chem. Chem. Phys. , 22 , 17677 ( 2020 ). 10.1039/D0CP02834G CASPubMedWeb of Science®Google Scholar Alburquerque , P. R. , Ramachandran , B. R. , Junk , T. , and Karsili , T. N. V. , J. Phys. Chem. A , 124 , 2530 ( 2020 ). 10.1021/acs.jpca.9b10892 CASPubMedWeb of Science®Google Scholar Voronin , V. V. , Ledovskaya , M. S. , Rodygin , K. S. , and Ananikov , V. P. , Org. Chem. Front. , 7 , 1334 ( 2020 ). 10.1039/D0QO00202J CASWeb of Science®Google Scholar Zhu , C. J. , Kuniyil , R. , Jei , B. B. , and Ackermann , L. , ACS Catal. , 10 , 4444 ( 2020 ). 10.1021/acscatal.9b05413 CASWeb of Science®Google Scholar Stockhammer , L. , Schorgenhumer , J. , Mairhofer , C. , and Waser , M. , Eur. J. Org. Chem. , 82 ( 2021 ). Google Scholar Chen , M. Y. , Pannecoucke , X. , Jubault , P. , and Besset , T. , Org. Lett. , 22 , 7556 ( 2020 ). 10.1021/acs.orglett.0c02750 CASPubMedWeb of Science®Google Scholar Organic Reaction Mechanisms 2020 ReferencesRelatedInformation