Trabalho - Cronograma Físico 10 Financeiro

Folha Nº 2 Local do Imóvel Total de fls Nome Nome Assinatura Assinatura Data Data Registro CREA Pavi mento Coberta Coberta Coberta padrão Equiva padrão Equiva padrão Equiva Real lente de Real De cons Real lente de Real De cons Real lente de Real De cons Real De cons cons trução cons trução cons trução trução trução 2 3 2 4 trução 7 8 7 9 trução 12 13 12 14 5 10 15 6 11 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 X SUBSOLO 19665 9833 19665 9833 29301 14651 29301 14651 1599 710 355 2309 1954 51275 26437 1 TÉRREO 14490 7245 14490 7245 24654 12327 24654 12327 10110 1394 697 11504 10807 50648 30379 1 PAVTIPO 23823 23823 23823 2645 2645 2645 26468 26468 7 CASA DE MÁQ 1560 746 373 2306 1933 2306 1933 1 CAIXA DAGUA 1560 780 1560 780 1560 780 1 Totais 166761 34155 17078 200916 183839 000 53955 26978 53955 26978 31784 4410 2205 36194 291065 291065 24480500 S Área real global total da coluna 17 Área de construção global total da coluna 18 pavimento ou descoberta Totais QUANTIDADE número de pavimentos idênticos Totais Coberta de pa drão diferente ou descoberta Área de uso comum Área de uso comum Área de divisão proporcional Área de divisão não proporcional ou descoberta drão diferente INFORMAÇÕES PARA ARQUIVO NO REGISTRO DE IMÓVEIS LEI 4591 161264 ART 32 E NBR 12721 Quadro I Cálculo das Áreas nos Pavimentos e das Áreas Globais Colunas 1 a 18 Totais Coberta de pa drão diferente MARIANA REIS OLIVEIRA do Área privativa Coberta de pa Adotar numeração segui da do quadro I ao VIII Área Incorporador Profissional responsável pelo cálculo e pela obra Folha Nº3 Local do Imóvel Adotar numeração segui Ed TCC da do quadro I ao VIII Total de fls Nome Nome Assinatura Assinatura Data Data Registro no CREA Coefi ciente Uni de pro dades Total porcio Coberta Coberta área nali Coberta padrão padrão de cons dade padrão Equiva De cons De Real Equiva Real De cons Real Equiva Real De cons trução 30 Real lente de Real trução Real Constru lente de trução lente de trução cons ção cons 20 21 20 22 cons 25 26 25 27 24 29 S30 31 X S12 31X S13 trução 32 33 32 34 232835 30 36 trução trução 31X S14 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 X Apt 01 01 vaga 8018 1035 5175 9053 85355 16352 8176 1635 818 9353 00443655 1410 196 098 1606 1508 12294 7 Apt 02 01 vaga 7922 1035 5175 8957 84395 16352 8176 1635 818 9257 00439102 1396 194 097 1589 1492 12181 7 Apt 03 01 vaga 7883 1035 5175 8918 84005 16352 8176 1635 818 9218 00437252 1390 193 096 1583 1486 12136 7 Vagas Garagem 1035 5175 1035 5175 16352 8176 1635 818 1335 00063328 201 028 014 229 215 2899 12 166761 34155 17078 200916 183839 000 53960 26980 53960 26980 210819 10000000 31784 4410 2205 36194 33989 291070 unidade ou descoberta ou descoberta ou descoberta drão diferente Totais drão diferente Totais drão diferente QUANTIDADE número de unidades idênticas Área privativa Área de uso comum Área de uso comum Área Coberta de pa Coberta de pa Coberta de pa de Totais MARIANA REIS OLIVEIRA S Incorporador Profissional responsável pelo cálculo e pela obra INFORMAÇÕES PARA ARQUIVO NO REGISTRO DE IMÓVEIS LEI 4591 161264 ART 32 E NBR 12721 Quadro II Cálculo das Áreas das Unidades Autônomas Colunas 19 a 38 Área de divisão não proporcional Área de divisão proporcional Palladiumcatalyzed Boronic Acid Addition to Imines via Transmetalation with Lithium Triolborate Yunwei Gu Richard A Friesner and James P Morken Department of Chemistry Columbia University 3000 Broadway New York New York 10027 United States Department of Chemistry Boston College 2609 Beacon Street Chestnut Hill Massachusetts 02467 United States Supporting Information Placeholder ABSTRACT A procedure is described whereby the reactions of imines with unactivated boronic acids are catalysed by palladiumII monks and mediated by the organoboron triolborate anion The active species was found to be a palladiumIIiminyl complex that undergoes organoboronmediated addition to an electrophilic center with release of the product amine The conditions are minimalist and operationally simple with both Naryl and Nalkyl imines viable substrates The reaction proceeds well with boronic acids having alkyl aryl and heteroaryl substituents and in the presence of functional groups such as bromo vinyl and allyl Coupling is compatible with functionalized aromatic and aliphatic substrates and can be performed with imines derived form aldehydes or ketones Latestage functionalization of biorelevant heterocycles is also feasible KEYWORDS Palladium catalysis Imines Organoboron Amines Transmetalation Crosscoupling Borocatalysis The construction of new carbonnitrogen bonds CN is indispensable in organic synthesis because amines feature prominently in many biologically active molecules pharmaceuticals and natural products1 Among the various synthetic approaches for amine formation the exclusive functionalization of imines remains a particularly attractive strategy because imines are readily available structural varied and often exhibit good stability and versatile reactivity2 The most common mode for imine functionalization involves addition of nucleophiles to the CN double bond for which many special examples have been demonstrated3 However these methods are limited by the nucleophile tolerance and availability and typically generate stoichiometric metalcontaining waste Transitionmetalcatalyzed imine functionalization by formation of CN bond is a powerful tool in organic synthesis and has attracted great attention in recent years4 The advent of transitionmetal complexes as catalysts common in CC and CN coupling reactions undoubtedly provides a way to construct CN bonds via catalytic imine functionalization Although significant efforts have been made on Pdcatalyzed imine functionalization5 most of them traditionally focus on precursors such as imino halides5a hydrazones5e nitrogen nucleophiles5b Ntosylhydrazones5gNnitrosoamines5h or additionelimination reactions5d while direct transmetalation from organoboron to Pd under mild conditions has rarely been reported Compared with other commonly used organometallic reagents organoboron species have obvious advantages such as low cost low toxicity and wide functional group compatibility Among various organoboron reagents boronic acids are particularly attractive due to their ease of preparation and practical use6 Herein we report a novel PdIIcatalyzed boronic acid addition to imines through direct transmetalation with lithium triolborate leading to facile preparation of diverse aryl and alkyl amines Scheme 1 ORGANIC LETTERS Scheme 1 PdCatalyzed Boronic Acid Addition to Imines How to run this reaction PdOAc2 POS mol Base 50 mol L 50 mol Boronic acid 1 12 equiv Imines 2 1 equiv MeOH rt100C 12h Ar 6 Results and Discussion At the outset of this study we examined the addition of phenylboronic acid to an Nbenzylideneaniline a representative imine substrate in the presence of PdOAc2 as the catalyst Under optimized conditions with Li triolborate LiPhBCat3 as the boron reagent the desired secondary amine was obtained in 92 yield after 12 h at room temperature Table 1 entry 1 Presence of the Pd catalyst was essential as only a trace amount of product was formed in its absence entry 2 Reactions with other boron reagents such as PhBpin PhBneop PhBF3K and PhBOH2 gave lower or no activity entries 36 The addition of a base such as K2CO3 or NaOH was found to improve the yield entries 7 and 8 and the sterically hindered ligand L1 was optimal among the tested ligands entries 911 The reaction proceeded smoothly in methanol while other solvents such as dichloromethane or toluene led to decreased yields entries 12 and 13 Next the scope of the reaction with respect to the imine substrate was explored A series of Naryl and Nalkyl imines were synthesized and subjected to the optimized reaction conditions Both electronrich and electronpoor substituents on the aryl ring were tolerated affording the corresponding amines in good to excellent yields Notably imines derived from aliphatic aldehydes also reacted successfully providing access to secondary amines with diverse alkyl groups The functional group tolerance was examined by including substrates containing halogens vinyl and allyl groups all of which were compatible with the reaction conditions Finally the application of this methodology to the latestage functionalization of complex molecules was demonstrated through the successful modification of biologically relevant heterocycles indicating the potential utility of this reaction in pharmaceutical synthesis In summary a new palladiumcatalyzed methodology for the addition of boronic acids to imines via lithium triolboratemediated transmetalation is presented This protocol offers a straightforward and efficient route to aryl and alkyl amines under mild conditions with a broad substrate scope and good functional group tolerance highlighting its practical applications in organic synthesis Supporting Information Experimental procedures characterization data and NMR spectra for all new compounds are available free of charge in the Supporting Information Corresponding Author Email jmorkenbcedu ORCID Yunwei Gu 0000000212345678 James P Morken 0000000387654321 Author Contributions The manuscript was written through contributions of all authors All authors have approved the final version of the manuscript Notes The authors declare no competing financial interest ACKNOWLEDGMENTS This work was supported by the National Science Foundation Grant CHEXXXXX and the National Institutes of Health Grant R01 GMXXXXX The authors thank Dr A Smith for helpful discussions REFERENCES 1 Hartwig J F Organotransition Metal Chemistry From Bonding to Catalysis University Science Books Sausalito 2010 2 Seebach D Methods of Reactivity Umpolung Academic Press London 1979 3 Denmark S E Thorarensen A Org Lett 1999 1 111114 4 Miyaura N Chevron Science Press 2017 2 100115 5 selected examples on Pdcatalyzed imine functionalization a Zhang X Chen X J Am Chem Soc 2012 134 184 b Lou C Lee K J Org Chem 2015 80 1234 c Wang Y Ding C Zhao Q Org Biomol Chem 2018 16 5678 d Chen J Li G Chem Eur J 2020 26 7890 e Gupta A Fuchs P Chem Rev 2021 121 7000 f Lee T Kim S Park J Chem Sci 2022 13 1500 g Thompson R Wang Z Org Lett 2023 25 1600 h Bum DM Choi Y Angew Chem Int Ed 2019 58 9321 6 Brown H C Rao B C S Boronic Acids Preparation and Applications in Organic Synthesis Wiley New York 2012 Quadro III AVALIAÇÃO DO CUSTO GLOBAL E UNITÁRIO DA CONSTRUÇÃO Folha Local do Imóvel Adotar numeração Ed TCC seguida do QI ao VIII Total de fls Nome Nome Assinatura Assinatura Data Data Registro CREA 1 Projeto Padrão lei 4591 art 531 que mais se assemelha ao da incorporação projetada Quartos Salas Banheiros ou WC R8 NORMAL 7 244805 2 1 2 4 Áreas Globais do prédio projetado 41 Área real privativa global QI S 5 200916 m² 42 Área real de uso comum global 90149 m² 43 Área real global QI S 17 291065 m² 44 Área de construção privativa global QI S 6 183839 m² 45 Área de construção de uso comum global 318043 m² 46 Área de construção global QI S 18 244805 m² 5 Área básica global da edificação 46 X custo unitário básico 3 51 Composição do custo global básico da edificação 511 Custo básico de materiais e outros 5 x material do CUB 4573 512 Custo básico de mão de obra 5 x mão de obra do CUB 5058 6 Parcelas adicionais não considerada no projeto padrão 61 Fundações especiais no projetopadrão foram consideradas fundações diretas a 250 m R 62 Elevador 6 paradas R 8000000 63 Equipamento e instalações de 631 Fogões R 632 Aquecedores R 633 Bombas de recalque R 240000 634 Incineração R 635 Ar condicionado R 636 Calefação R 637 Ventilação e exaustão R 638 Garagem R 639 Payground R 64 Obras e serviços complementares R 641 Terraplanagem R 642 Urbanização R 643 Recreação piscinas campos de esporte R 644 Ajardinamento R 645 Ligações de serviços públicos art51 R 646 Instalação e regulamentação do condomínio R 647 R 648 R 65 Outros serviços discriminados em anexo R 7 1º Subtotal R 606658478 R 8 Impostos e taxas 9 Outros projetos não constantes na nota deste quadro R 91 Honorários do autor do projeto arquitetônico R 350000 92 Honorários do autor do projeto estrutural R 250000 93 Honorários do autor do projeto de instalações R 230200 10 2º Subtotal R 607488678 R 11 Remuneração do construtor R 12 Remuneração do incorporador R 13 Custo global da construção R 607488678 14 Preço por m2 da construção 13 46 R R 248152 NB Os valores correspondentes aos itens 91 92 e 93 quando ainda não contratados poderão ser calculados de acordo com as tabelas fornecidas pelos respectivos órgãos de classe Avaliação do custo global da construção e do preço por m2 da construção 273656770 R 302680066 R MARIANA REIS OLIVEIRA Número de pavimentos 1 3 Custo unitário básico para o mês de AGOSTO2013 244447 R por m² INFORMAÇÕES PARA ARQUIVO NO REGISTRO DE IMÓVEIS LEI 4591 161264 ART 32 E NBR 12721 Profissional responsável pelo cálculo e pela obra Incorporador INFORMAÇÕES PRELIMINARES 598418478 R CLASSIFICAÇÃO GERAL USO RESIDENCIAL Padrão de acabamento Designação QI S 10 S 15 QI S 11 S 16 Área equivalente total do projeto padrão adotado Dependências de uso privativo da unidade autônoma Quartos de empregados